Thermosetting compositions, thermal latent acid catalysts, methods of coating and coated articles

ABSTRACT

Thermosetting composition comprises a compound having in the molecule two or more carboxyl groups blocked by a vinyl ether compound, a vinyl thioether compound or a hetero compound having a vinyl type double bond and oxygen or sulfur as the hetero atom, a compound having two or more reactive functional groups which can form a chemical bond with the blocked carboxyl compound by heating, a specific vinyl ether or vinyl thioether and a thermal latent acid catalyst. The blocked carboxyl group of the first compound and the reactive functional group of the second compound may be comprised in the same molecule. The thermosetting composition gives cured products having excellent chemical properties, physical properties, weathering resistance and storage stability and is advantageously utilized for coating compositions, ink, adhesive and molded plastics.

This application is a continuation-in-part of application Ser. No.07/680,356, filed Apr. 4, 1991, now U.S. Pat. No. 5,352,740.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel thermosetting compositions,thermal latent catalysts, methods of coating and coated articles. Moreparticularly, it relates to novel thermosetting compositions havingexcellent chemical properties, physical properties, weatheringresistance and storage stability and methods of coating to provide a topcoating having the excellent properties as described above and excellentappearance by using the thermosetting compositions as the top coatingmaterial.

2. Description of the Prior Art

It is generally known that thermosetting compositions can be preparedfrom compounds having carboxyl groups and compounds having reactivefunctional groups which can form chemical bonds with the carboxyl groupsby heating, such as epoxy group, oxazoline group, silanol group,alkoxysilane group, hydroxyl group, amino group, imino group, isocyanategroup, blocked isocyanate group, cyclocarbonate group, vinyl ethergroup, vinyl thioether group, aminomethylol group, alkylatedaminomethylol group, acetal group and ketal group. The thermosettingcompositions give cured products having excellent chemical properties,physical properties and weathering resistance and are widely utilized inthe field of coating composition, ink, adhesive and molded plastics.

As thermosetting compositions described above, for example, compositionscomprising combinations of carboxyl group and epoxy group have beendisclosed in Laid Open Japanese Patent Application Showa 51-114429, LaidOpen European Patent Application 29595 and U.S. Pat. Nos. 4,371,667,4,650,718, 4,681,811, 4,703,101 and 4,764,430.

Compositions comprising combinations of carboxyl group and oxazolinegroup, as other examples, have been disclosed in U.S. Pat. No. 3,505,297and Laid Open Japanese Patent Applications Showa 60-88038 and Heisei2-115238.

The thermosetting compositions give cured products having excellentchemical properties, physical properties and weathering resistance andare widely utilized in the field of coating composition, ink, adhesiveand molded plastics.

However, the reactivity between the carboxyl group and the reactivefunctional groups is generally very high and compositions in whichcompounds having carboxyl groups and compounds having the reactivefunctional groups are mixed together have a problem that thecompositions are often gelled during storage and the period suitable forservice is short.

Compounds comprising carboxyl groups conventionally utilized forthermosetting compositions described above have problems that solubilityto generally used solvents is low and that compatibility with thecompounds having reactive groups with the carboxyl group is inferiorbecause of the tendency of the carboxyl group to form strong hydrogenbonds. When thermosetting compositions comprising these kinds ofcompounds are utilized as top coating materials, they naturally haveproblems that preparation of high solid coating materials is difficultand that appearance of the finished coating is inferior.

For the purpose of solving these problems, it was proposed that carboxylgroup was blocked by converting it to tertiary-butyl ester and the freecarboxyl group was regenerated by elimination of isobutene by heating(Laid-Open Japanese Patent Application Heisei 1-104646). However, thismethod required a high temperature, such as 170°-200° C., for the heatdecomposition of the tertiary-butyl ester and pock marks which were madeby foaming and degassing of isobutene formed by the decompositionremained on the cured surface of the coating. Thus, this method is notsatisfactory.

SUMMARY OF THE INVENTION

The present invention accordingly has an object to provide thermosettingcompositions which give cured products having excellent chemicalproperties, physical properties, weathering resistance and storagestability and can be utilized as high solid one component coatingmaterials. Another object of the invention is to provide thermal latentacid catalysts which give excellent storage stability and excellentcuring property simultaneously to the thermosetting compositions.

Still other objects of the invention are to provide methods of coatingwhich discharge little amount of organic solvents into air and giveexcellent appearance to the finished articles and to provide articlesprepared by utilizing the methods of coating.

Extensive investigations undertaken by the present inventors with theobjects described above lead to a discovery that the objects can beachieved by a composition comprising, essentially, (A) a compound havingin the molecule two or more carboxyl groups which are blocked by aspecific vinyl ether group, vinyl thioether group or heterocyclic grouphaving vinyl type double bond and oxygen or sulfur as the hetero atomcomponent; essentially, (B) a compound having in the molecule two ormore reactive functional groups which can form chemical bonds with theblocked carboxyl groups by heating, essentially, (E) a specific vinylether or a specific vinyl thioether and, optionally, (C) a thermallatent acid catalyst which is activated during curing by heating; by acomposition comprising, essentially, (D) a self-crosslinking compoundhaving in the molecule one or more blocked carboxyl groups and one ormore reactive functional groups which can form chemical bonds with theblocked carboxyl groups by heating, essentially, (E) a specific vinylether or a specific vinyl thioether, optionally, (C) a thermal latentacid catalyst described above and, optionally, the compound (A) and/orthe compound (B); by a composition comprising, essentially, the compound(A), essentially, the compound (B) and, essentially, (F) a specificthermal latent acid catalyst which is activated during curing byheating; by a composition comprising, essentially, the compound (D) and,essentially, the compound (F) and, optionally, the compound (A) and/orthe compound (B); and by a composition comprising, essentially, thecompound (A), essentially, (G) a compound having two or more oxazolinegroups in the molecule and, optionally, (C) a thermal latent acidcatalyst which is activated during curing by heating. It was alsodiscovered that the method of coating utilizing the thermosettingcomposition having the advantageous properties as the top coatingmaterial discharges little amount of organic solvents into air and givesexcellent appearance to the finished articles. The present invention wascompleted on the basis of the discovery described above.

Thus, the thermosetting compositions of the invention comprise:essentially, (A) a compound having in the molecule two or morefunctional groups of the formula [1]: ##STR1## wherein R¹, R² and R³ arerespectively selected from the group consisting of a hydrogen atom andan organic group of 1 to 18 carbon atoms, R⁴ is an organic group of 1 to18 carbon atoms, Y¹ is selected from the group consisting of an oxygenatom and a sulfur atom and R³ and R⁴ may be bonded with each other toform a heterocyclic structure which comprises Y¹ as the hetero atomcomponent; essentially, (B) a compound having in the molecule two ormore reactive functional groups which can form chemical bonds with thefunctional groups of the compound (A) by heating; essentially, (E) acompound of the formula [2]: ##STR2## wherein R¹, R², R³, R⁴ and Y¹ havethe same meaning as in the compound (A); and, optionally, (C) a thermallatent acid catalyst which is activated during curing of the compositionby heating.

The thermosetting composition of the invention also comprise:essentially, (D) a self-crosslinking compound having in the molecule (a)one or more functional groups of the formula [3]: ##STR3## wherein R⁵,R⁶ and R⁷ are respectively selected from the group consisting of ahydrogen atom and an organic group of 1 to 18 carbon atoms, R⁸ is anorganic group of 1 to 18 carbon atoms, Y² is selected from the groupconsisting of an oxygen atom and a sulfur atom and R⁷ and R⁸ may bebonded with each other to form a heterocyclic structure which comprisesY² as the hetero atom component; and (b) one or more reactive functionalgroups which can form chemical bonds with the functional groups (a) byheating; essentially, (E) a compound of the formula [2]: ##STR4##wherein R¹, R², R³, R⁴ and Y¹ have the same meaning as in the compound(A); optionally, (C) a thermal latent acid catalyst which is activatedduring curing of the composition by heating; and, optionally, thecompound (A) described above and/or (B) a compound having in themolecule two or more reactive functional groups which can form chemicalbonds by heating with either one or both of the functional group of theformula [3] and the functional group of the formula [1].

The thermosetting composition of the invention also comprise:essentially, (A) a compound having in the molecule two or morefunctional groups of the formula [1]: ##STR5## wherein R¹, R² and R³ arerespectively selected from the group consisting of a hydrogen atom andan organic group of 1 to 18 carbon atoms, R⁴ is an organic group of 1 to18 carbon atoms, Y¹ is selected from the group consisting of an oxygenatom and a sulfur atom and R³ and R⁴ may be bonded with each other toform a heterocyclic structure which comprises Y¹ as the hetero atomcomponent; essentially, (B) a compound having in the molecule two ormore reactive functional groups which can form chemical bonds with thefunctional groups of the compound (A) by heating; and essentially, (F)at least one thermal latent acid catalyst selected from the groupconsisting of a complex compound made from a Lewis acid and a Bronstedacid and a complex compound made from a Lewis acid and a Bronsted salt.

The thermosetting composition of the invention also comprise:essentially, (D) a self-crosslinking compound having in the molecule (a)one or more functional groups of the formula [3]: ##STR6## wherein R⁵,R⁶ and R⁷ are respectively selected from the group consisting of ahydrogen atom and an organic group of 1 to 18 carbon atoms, R⁸ is anorganic group of I to 18 carbon atoms, Y² is selected from the groupconsisting of an oxygen atom and a sulfur atom and R⁷ and R⁸ may bebonded with each other to form a heterocyclic structure which comprisesY² as the hetero atom component; and (b) one or more reactive functionalgroups which can form chemical bonds with the functional groups (a) byheating; essentially, (F) at least one thermal latent acid catalystselected from the group consisting of a complex compound made from aLewis acid and a Bronsted acid and a complex compound made from a Lewisacid and a Bronsted salt; and, optionally, the compound (A) describedabove and/or (B) a compound having in the molecule two or more reactivefunctional groups which can form chemical bonds by heating with eitherone or both of the functional group of the formula [3] and thefunctional group of the formula [1].

The thermosetting composition of the invention also comprise:essentially, (A) a compound having in the molecule two or morefunctional groups of the formula [1]: ##STR7## wherein R¹, R² and R³ arerespectively selected from the group consisting of a hydrogen atom andan organic group of 1 to 18 carbon atoms, R⁴ is an organic group of 1 to18 carbon atoms, Y¹ is selected from the group consisting of an oxygenatom and a sulfur atom and R³ and R⁴ may be bonded with each other toform a heterocyclic structure which comprises Y¹ as the hereto atomcomponent; essentially, (G) a compound having two or more oxazolinegroups in the molecule; and, optionally, (C) a thermal latent acidcatalyst which is activated during curing of the composition by heating.

The thermal latent acid catalysts of the invention comprise a complexcompound made from at least one compound selected from Lewis acids andat least one compound selected from Bronsted salts. The thermal latentacid catalysts of the invention also comprise a complex compound madefrom at least one compound selected from Lewis acids and at least onecompound selected from Bronsted acids.

The articles of the invention are coated by the methods of coating ofthe invention described above.

Other and further objects, features and advantages of the invention willappear more fully from the following description.

DETAILED DESCRIPTION OF THE INVENTION

The invention will be explained in detail in the following.

The compound (A) in the thermosetting composition of the invention hasin the molecule two or more, preferably from 2 to 50, functional groupsof the following formula [1]: ##STR8## wherein R¹, R², R³, R⁴ and Y¹have the same meaning as described above. The functional group havingthe formula [1] is easily prepared by reaction of carboxyl group with avinyl ether, a vinyl thioether or a heterocyclic compound having oxygenor sulfur as the hetero atom and having a vinyl type double bond whichis described by the formula [2]: ##STR9## wherein R¹, R², R³, R⁴ and Y¹have the same meaning as described above.

In the formula [1] and formula [2], R¹, R² and R³ are respectivelyselected from the group consisting of a hydrogen atom and an organicgroup, such as alkyl group, aryl group and alkaryl group of 1 to 18carbon atoms, R⁴ is an organic group, such as alkyl group, aryl groupand alkaryl group of 1 to 18 carbon atoms. The organic groups may havesubstituted groups in the molecule and R³ and R⁴ may, by bondingtogether, form a heterocyclic structure with or without substituents andhaving Y¹ as the hetero atom component.

Examples of the compound of the formula [2] are: aliphatic vinyl ethers,such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether,n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether,2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and the like; aliphaticvinyl thioethers, such as methyl vinyl thioether, ethyl vinyl thioether,isopropyl vinyl thioether, n-propyl vinyl thioether, n-butyl vinylthioether, isobutyl vinyl thioether, 2-ethylhexyl vinyl thioether,cyclohexyl vinyl thioether and the like; cyclic vinyl ethers, such as2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran,3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran,3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran,sodium 3,4-dihydro-2H-pyran-2-carboxylate and the like; and cyclic vinylthioethers, such as 2,3-dihydrothiophene, 3,4-dihydrothiophene,2,3-dihydro-2H-thiopyran, 3,4-dihydro-2H-thiopyran,3,4-dihydro-2-methoxy-2H-thiopyran,3,4-dihydro-4,4-dimethyl-2H-thiopyran-2-one,3,4-dihydro-2-ethoxy-2H-thiopyran, sodium3,4-dihydro-2H-thiopyran-2-carboxylate and the like.

The compound (A) is prepared by the reaction of a compound having two ormore, preferably 2 to 50, carboxyl groups in the molecule with thecompound having the formula [2]. Examples of the compound having two ormore carboxyl groups in the molecule are: aliphatic polycarboxylic acidsof 2 to 22 carbon atoms, such as succinic acid, adipic acid, azelaicacid, sebacic acid, decamethylenedicarboxylic acid and the like;aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid,terephthalic acid, trimellitic acid, pyromellitic acid and the like;alicyclic polycarboxylic acids, such as tetrahydrophthalic acid,hexahydrophthalic acid, methylhexahydrophthalic acid and the like;resins having two or more carboxyl groups in the molecule, such aspolyester resins, acrylic resins, polybutadiene resins modified withmaleic acid and the like resins having two or more carboxyl groups inthe molecule.

The compound having two or more carboxyl groups in the molecule isprepared by: (1) half-esterification of a polyol having two or more,preferably 2 to 50, hydroxyl groups in the molecule with an acidanhydride; (2) addition of a polyisocyanate compound having two or more,preferably 2 to 50 isocyanate groups in the molecule with ahydroxycarboxylic acid or an amino acid; (3) polymerization of anα,β-unsaturated monomer having carboxyl group or copolymerization of theα,β-unsaturated monomer with other α,β-unsaturated monomers; (4)preparation of polyester resin having carboxyl groups and the like othermethods.

Examples of the polyol having two or more hydroxyl groups are: ethyleneglycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol,pentanediol, dimethylbutanediol, hydrogenated bisphenol A, glycerol,sorbitol, neopentyl glycol, 1,8-octanediol, 1,4-cyclohexanedimethanol,2-methyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol,trimethylolethane, trimethylolpropane, pentaerythritol, quinitol,mannitol, tris-hydroxyethyl isocyanurate, dipentaerythritol and thelike; addition products of the polyhydric alcohol with a lactone, suchas γ-butyrolactone and ε-caprolactone and the like, by ring opening ofthe lactone; addition products of the polyhydric alcohol with anisocyanate, such as tolylene diisocyanate, diphenylmethane diisocyanate,hexamethylene diisocyanate, isophorone diisocyanate and the like, inexcess amount of the alcohol; addition products of the polyol with adivinyl ether, such as ethylene glycol divinyl ether, polyethyleneglycol divinyl ether, butanediol divinyl ether, pentanediol divinylether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl etherand the like, in excess amount of the alcohol; addition products of thepolyol with an alkoxysilane compound, such as KR-213®, KR-217®, KR-9218®(products of Shinetsu Chemical Co., Ltd.), in excess amount of thealcohol; and the like other compounds.

Examples of the acid anhydride which reacts with the polyol having twoor more hydroxyl groups in the molecule are: acid anhydrides ofpolycarboxylic acids, such as succinic acid, glutaric acid, adipic acid,azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalicacid, maleic acid, trimellitic acid, pyromellitic acid,tetrahydrophthalic acid, hexahydrophthalic acid and the like.

Examples of the polyisocyanate compound having two or more isocyanategroups in the molecule are: p-phenylene diisocyanate, biphenyldiisocyanate, tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 1,4-tetramethylene diisocyanate, hexamethylenediisocyanate, 2,2,4-trimethylhexane- 1,6-diisocyanate,methylene-bis-(phenyl isocyanate), lysine methyl ester diisocyanate,bis-(isocyanatoethyl) fumarate, isophorone diisocyanate,methylcyclohexyl diisocyanate,2-isocyanatoethyl-2,6-diisocyanatohexanoate, biuret derivatives of thesepolyisocyanates, isocyanurate derivatives of these polyisocyanates andthe like compounds.

Examples of the hydroxycarboxylic acid which reacts with thepolyisocyanate compound are: lactic acid, citric acid, hydroxypivalicacid, 12-hydroxystearic acid, malic acid and the like. Examples of theamino acid which reacts with the polyisocyanate compound are:DL-alanine, L-glutamic acid, glycine, L-teanine, glycylglycine,aminocaproic acid, L-aspartic acid, L-citrulline, L-arginine, L-leucine,L-serine and the like.

Examples of the α,β-unsaturated monomer having carboxyl group which arepolymerized or copolymerized are: acrylic acid, methacrylic acid,itaconic acid, mesaconic acid, maleic acid, fumaric acid and the like.Examples of the other α,β-unsaturated monomer which is copolymerizedwith the α,β-unsaturated monomer having carboxyl group are: methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,sec-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, stearyl (meth)acrylate, styrene, α-methylstyrene,p-vinyltoluene, acrylonitrile and the like.

The polyester resin having carboxyl groups is easily prepared accordingto the conventional method of preparation of polyester resins by usingexcess amount of polyacid in relation to the amount of polyol.

The reaction of the compound having two or more carboxyl group in themolecule with the compound having the formula [2] is generally performedat a temperature between the ambient temperature and 100° C. in thepresence of an acid catalyst.

Either a single kind of the compound (A) or a combination of two or morekinds of the compound (A) may be utilized in the invention.

The compounds (B) utilized in the thermosetting composition of theinvention are compounds .having in the molecule two or more, preferablyfrom 2 to 50, reactive functional groups which can form chemical bondsby the reaction with the regenerated carboxyl group formed from theblocked carboxyl group [1] of the compound (A) by heating. The kind ofthe reactive functional group is not particularly limited so long as itsatisfies the condition described above. Preferable examples of thereactive functional group are: epoxy group, oxazoline group, silanolgroup, alkoxysilane group, hydroxyl group, amino group, imino group,isocyanate group, blocked isocyanate group, cyclocarbonate group, vinylether group, vinyl thioether group, aminomethylol group, alkylsubstituted aminomethylol group, acetal group, ketal group and the likegroups. The compound (B) may have either a single kind or two or morekinds of the reactive functional groups in the molecule.

Examples of the compound of (B) are: compounds having epoxy group, suchas epoxy resins of bisphenol type, alicyclic epoxy resins, homopolymersand copolymers of glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate and the like compounds, polyglycidyl compounds obtainedby the reaction of epichlorohydrine with polycarboxylic acids or polyolsand other like compounds; compounds having oxazoline group, such asoxazoline compounds having an oxazoline ring connected to an alkyl chainlike 1,2-bis(2-oxazolinyl-2)ethane, 1,4-bis(2-oxazolinyl-2)butane,1,6-bis(2-oxazolinyl-2)hexane, 1,8-bis(2-oxazolinyl-2)octane,1,4-bis(2-oxazolinyl-2)cyclohexane and the like, oxazoline compoundshaving two oxazoline rings connected to an aromatic ring like benzenering like 1,2-bis(2-oxazolinyl-2)benzene,1,3-bis(2-oxazolinyl-2)benzene, 1,4-bis(2-oxazolinyl-2)benzene,5,5'-dimethyl-2,2'-bis(2-oxazolinyl-2)benzene,4,4,4',4'-tetramethyl-2,2'-bis(2-oxazolinyl-2)benzene,1,2-bis(5-methyl-2-oxazolinyl-2)benzene,1,4-bis(5-methyl-2-oxazolinyl-2)benzene and the like. bis-(2-oxazoline)compounds like 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline),2,2 '-bis(5-methyl-2-oxazoline) and the like, polyfunctional oxazolinecompounds obtained by the reaction of hydroxyalkyl-2-oxazoline with thepolyisocyanate compounds described above, compounds comprising oxazolinegroup like polymers and copolymers of 2-vinyl-2-oxazoline,2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline,2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline,2-isopropenyl-5-ethyl-2-oxazoline and the like, commercial compoundscomprising oxazoline group like CX-RS-1200®, CX-RS-3200® (products ofNippon Shokubai Co., Ltd.) and the like other compounds having oxazolinegroup; compounds having silanol group or alkoxysilane group, such ascondensation products of a compound having the formula [4]:

    (R.sup.10).sub.n Si(OR.sup.11).sub.4-n                     [ 4]

wherein R¹⁰ and R¹¹ are respectively selected from the group consistingof alkyl group of 1 to 18 carbon atoms and aryl group of 1 to 18 carbonatoms and n is 0, 1 or 2, homopolymers and copolymers of α,β-unsaturatedsilane compounds, like acryloyloxypropyltrimethoxysilane,methacryloyloxypropyltrimethoxysilane,methacryoyloxy-propyl-tri-n-butoxysilane and the like, hydrolysisproducts of these compounds and the like; compounds having hydroxylgroup, such as aliphatic polyols, phenols, polyalkyleneoxyglycols,homopolymers and copolymers of α,β-unsaturated compounds, like2-hydroxyethyl-(meth)acrylates, 2-hydroxypropyl (meth)acrylate and thelike, addition products of ε-caprolactone with these polyhydroxylcompounds and the like; compounds having amino group, such as aliphaticdiamino compounds, aromatic diamino compounds, polyamino compoundsprepared by cyanoethylation and reduction of the compounds havinghydroxyl group and the like; compounds having imino group, such asaliphatic polyimino compounds, aromatic polyimino compounds and thelike; compounds having isocyanate group, such as p-phenylenediisocyanate, biphenyl diisocyanate, tolylene diisocyanate,3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylenediisocyanate, hexamethylene diisocyanate,2,2,4-trimethylhexane-1,6-diisocyanate, methylene-bis-(phenylisocyanate), lysine methyl ester diisocyanate, bis-(isocyanatoethyl)fumarate, isophorone diisocyanate, methylcylcohexyl diisocyanate,2-isocyanatoethyl 2,6-diisocyanatohexanoate, biuret derivatives andisocyanurate derivatives of these isocyanates, addition products ofthese isocyanates and the compounds having hydroxyl group and the like;compounds having blocked isocyanate group, such as compounds prepared byblocking the compounds having isocyanate group with phenols, lactams,active methylenes, alcohols, acid amides, imides, amines, imidazoles,ureas, imines, or oximes and the like compounds; compounds havingcyclocarbonate group, such as homopolymers and copolymers of3-(meth)acryloyloxypropylene carbonate, compounds having polyfunctionalcyclocarbonate groups prepared by the reaction of the compounds havingepoxy group with carbon dioxide and the like; compounds having vinylether group or vinyl thioether group, such as polyfunctional vinyl ethercompounds prepared by the reaction of the compounds having hydroxylgroup with halogenated alkyl vinyl ethers, polyvinyl ethers prepared bythe reaction of hydroxyalkyl vinyl ethers with compounds havingpolyfunctional carboxyl group or with the compounds having isocyanategroup, copolymer of vinyloxyalkyl (meth)acrylates with α,β-unsaturatedcompounds, vinyl thioethers corresponding to the vinyl ethers and thelike; compounds having aminomethylol groups or alkyl substitutedaminomethylol groups, such as melamine formaldehyde resins, glycolylformaldehyde resins, urea formaldehyde resins, homopolymers andcopolymers of α,β-unsaturated compounds having aminomethylol group oralkylated aminomethylol group and the like; compounds having acetalgroups or ketal groups, such as polyfunctional acetal compounds preparedby the reaction of polyfunctional ketones, polyfunctional aldehydes, orpolyfunctional vinyl ether compounds and the like compounds withalcohols or orthoacids esters, condensation products of thepolyfunctional acetal compounds with polyols, homopolymers andcopolymers of addition products of the vinyloxyalkyl (meth)acrylate withalcohols or orthoacid esters; and the like other compounds.

The compound (B) utilized in the invention may be either a compoundcomprising a single kind of functional group, such as the compoundsshown in the examples, or a compound comprising two or more kinds offunctional group in the molecule. Two or more kinds of the compound (B)may utilized together. However, when the functional groups of two ormore kinds are reactive between each other, the storage stability of thethermosetting composition is damaged and the utilization of suchcombination of the functional groups is undesirable. Examples of suchundesirable combination of functional groups are: combination of afunctional group selected from the group of epoxy group, isocyanategroup, vinyl ether group, vinyl thioether group, cyclocarbonate groupand silanol group with amino group or imino group, combination ofhydroxyl group with isocyanate group or vinyl ether group and the likeother combinations.

The thermosetting composition of the invention may comprise the compound(A) and the compound (B) or it may comprise compound (D), aself-crosslinking compound comprising (a) one or more, preferably from 1to 50, functional groups having the formula [3]: ##STR10## wherein R⁵,R⁶, R⁷, R⁸ and Y² have the same meaning as described above, and (b) oneor more, preferably from 1 to 50, reactive functional groups which canform chemical bond with the functional group (a) by heating. Thethermosetting composition of the invention may also comprise thecompound (D) and the compound (A) and/or the compound (B) and, in thiscase, the functional group of the compound (B) forms chemical bond withthe functional group of formula [1] and/or the functional group offormula [3] by heating.

Examples of the functional group (a) having the formula [3] of thecompound (D) are the same functional groups as the examples of thefunctional group having the formula [1] in the compound (A) alreadydescribed. Examples of the reactive functional group (b) are the samefunctional groups as the examples of the reactive functional groups ofcompound (B).

The compound (D) can be prepared from a compound comprising one or more,preferably from 1 to 50, carboxyl groups and one or more, preferablyfrom 1 to 50, reactive functional groups in the molecule by using thesame reaction as the reaction utilized in the preparation of thecompound (A). The compound (D) can also be prepared by copolymerizationof an unsaturated compound having the functional group of formula [3]with an unsaturated compound having the reactive functional group.

The compound (D) comprises the functional group of formula [3] and,furthermore, may comprise two or more kinds of the reactive functionalgroups in the same molecule. However, when the two or more kinds of thefunctional groups are reactive between each other, the storage stabilityof the thermosetting composition is damaged and the utilization of suchcombination of the functional groups is undesirable.

As (G) a compound comprising two or more oxazoline groups in themolecule utilized in the thermosetting composition of the invention, thecompounds having oxazoline group described above can be utilized.

The compound (G) provides the thermosetting composition with excellentlow temperature curing property and excellent hardness of the coating.

In the thermosetting composition of the invention, it is preferable thatat least one of the compounds (A) and/or the compound (B), at least oneof the compound (D) and the compound (A) and/or the compound (B) whichare utilized optionally or at least one of the compound (A) and/or (G)is a polymer of α,β-unsaturated compound or a polyester resin. It isalso preferable that equivalent ratio of the functional group of theformula [1] or the formula [3] and the reactive functional group to formchemical bond with the former functional group by heating utilized inthe thermosetting composition is adjusted in the range from 0.2:1.0 to1.0:0.2.

The functional groups having the formula [1] and the formula [3] in thecompound (A) and the compound (D) of the invention regenerate freecarboxyl group by heating and form chemical linkages with the reactivefunctional groups in the compound (B), the compound (D) and the compound(G). They can also react with the functional groups in the compound (B),the compound (D) and the compound (G) by addition between the functionalgroups and this addition reactions can contribute to decreasing amountof volatile organic substances discharged into air because the additionreactions are not accompanied with elimination reactions during thecrosslinking.

The compound (E) having the formula [2] utilized in the thermosettingcomposition of the invention blocks again the free carboxyl group whichhas been formed by hydrolysis of the blocked carboxyl group in thecompounds described above when water is present in the thermosettingcomposition and enhances the storage stability. The hydrolysis tends totake place particularly when the content of water in the thermosettingcomposition is 0.1 weight % or more and it is particularly effective inthis condition that the compound (E) is comprised in the composition.

As the compound having the formula [2] described above which is utilizedas the compound (E), a vinyl ether or a vinyl thioether of the same kindas that utilized for blocking the carboxyl group described above can beutilized. Examples of such a compound having the formula [2] are:aliphatic vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether,isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether,isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl etherand the like; aliphatic vinyl thioethers corresponding to the aliphaticvinyl ethers; cyclic vinyl ethers, such as 2,3-dihydrofuran,3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran,3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one,3,4-dihydro-2-ethoxy-2H-pyran, sodium 3,4-dihydro-2H-pyran-2 carboxylateand the like; cyclic vinyl thioethers corresponding to the cyclic vinylethers and the like compounds. Preferable examples among them are ethylvinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinylether and isobutyl vinyl ether.

The amount of the compound (E) utilized in the thermosetting compositionof the invention is preferably in the range from 0.1 to 20 weight % andmore preferably in the range from 1 to 10 weight % based on the totalamount of the thermosetting composition. When the amount is less than0.1 weight %, the effect to improve the storage stability is sometimesinsufficient and, when the amount is more than 20 weight %, the solidcontent of the thermosetting composition is decreased. Thus, amountsoutside of the specified range are not advantageous.

In the present invention, the thermal latent acid catalyst (C) whichshows activity in the curing condition at an elevated temperature may beoptionally comprised in the thermosetting composition for the purpose ofkeeping excellent storage stability of the composition for a long periodof time, promoting the curing reaction when the composition is cured ina short time at a rather low temperature and giving excellent chemicalproperties and physical properties to the cured products. It ispreferable that the thermal latent acid catalyst is a compound whichexhibit the activity at the temperature above 60° C. If the thermallatent acid catalyst shows the catalytic activity under 60° C., theprepared thermosetting composition has undesirable properties, such asincrease of viscosity during storage and formation of gel.

Preferred examples of the thermal latent acid catalyst (C) are compoundsprepared by neutralizing Bronsted acids or Lewis acids with Lewis bases,complex compounds formed from Lewis acids and Bronsted acids, complexcompounds formed from Lewis acids and Bronsted salts, esters of sulfonicacids, esters of phosphoric acid and onium compounds.

The Bronsted acid forming the thermal latent acid catalyst is asubstance showing acidity with dissociation of proton and preferablysulfuric acid, sulfonic acid, phosphoric acid, boric add, carboxylicacids and derivatives thereof.

Examples of the Bronsted acid are sulfuric acid, monoesters of sulfuricacid, phosphoric acid, monoesters and diesters of phosphoric acid,esters of polyphosphoric acid, monoesters and diesters of boric acid,sulfonic acids, carboxylic acids, halogenocarboxylic acids and the likeand, preferably, alkylbenzenesulfonic acids having 1 to 50 carbon atoms,such as dodecylbenzenesulfonic acid and the like, mono- ordihalogenocarboxylic acids, such as chloroacetic acid, dichloroaceticacid and the like, alkyl monoesters and diesters of phosphoric acidhaving 1 to 50 carbon atoms, such as monomethyl phosphate, dimethylphosphate and the like, and the like compounds. The Bronsted acid may beutilized singly or as a combination of two or more kinds.

The Lewis acid forming the thermal latent acid catalyst is a compoundhaving the property of accepting electrons and preferably a metal halideor a organometallic compound having the formula:

    (R.sup.9).sub.n -M

wherein R⁹ is a halogen atom or one or more kinds of organic groupsselected from the group consisting of alkyl groups, aryl groups, alkoxygroups and acyloxy groups of 1 to 20 carbon atoms and a carbonyl groupadjacent to an active methylene group, M is B, Mg, Al, Ca, Sn, Pb or atransition metal atom belonging to one of the 3A group to the 7A group,the 8 group, the 1B group and the 2B group in the fourth to the sixthperiod of the long Periodic Table and n is an integer in the range from1 to 6.

The metals forming the Lewis acid in the long Periodic Table describedabove are classified according to the method of nomenclature ofinorganic chemistry by IUPAC in 1988.

Examples of the Lewis acid are: metal halides, such as borontrifluoride, aluminum trichloride, titanium trichloride, titaniumtetrachloride, ferrous chloride, ferric chloride, zinc chloride, zincbromide, stannous chloride, stannic chloride, stannous bromide, stannicbromide and the like, organometallic compounds, such as trialkylboron,trialkylaluminum, dialkylaluminum halides, monoalkylaluminum halides,tetraalkyltin, aluminum actylacetonate, iron acetylacetonate, zirconiumacetylacetonate, dibutyltin acetylacetonate, dibutyltin dilaurate,dioctyltin ester maleate, magnesium naphthenate, calcium naphthenate,manganese naphthenate, iron naphthenate, cobalt naphthenate, coppernaphthenate, zinc naphthenate, zirconium naphthenate, lead naphthenate,calcium octanoate, manganese octanoate, iron octanoate, cobaltoctanoate, zinc octanoate, zirconium octanoate, tin octanoate, leadoctanoate, zinc laurate, magnesium stearate, aluminum stearate, calciumstearate, cobalt stearate, zinc stearate, lead stearate and the like,and other like compounds. The Lewis acid may be utilized singly or as acombination of two or more kinds.

The Lewis base utilized for neutralizing the Bronsted acid or the Lewisacid is a compound having the property of donating electrons. Examplesof the Lewis base are: amines, such as ammonia, triethylamine, pyridine,aniline, morpholine, N-methylmorpholine, pyrrolidine,N-methylpyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine,n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole,N,N-dimethylethanolamine, N,N-diethylethanolamine,N,N-dipropylethanolamine, N,N-dibutylethanolamine,N,N-dimethylisopropanolamine, N,N-diethylisopropanolamine,N,N-dipropylisopropanolamine, N,N-dibutylisopropanolamine,N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine,N-butyldiethanolamine, N-methyldiisopropanolamine,N-ethyldiisopropanolamine, N-propyldiisopropanolamine,N-butyldiisopropanolamine, triethanolamine, triisopropanolamine,tri-s-butanolamine and the like; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric acidtriamide and the like; sulfoxide compounds, such as dimethylsulfoxideand the like; ethers, such as diethylether, tetrahydrofuran and thelike; thioethers, such as dimethylsulfide and the like; esters ofphosphoric acid, such as trimethyl phosphate, triethylphosphate,tributyl phosphate and the like; esters of boric acid, such as trimethylborate and the like; esters of carboxylic acids, such as ethyl acetate,butyl acetate and the like; esters of carbonic acid, such as ethylenecarbonate and the like; trialkylphosphines, such as tributylphosphineand the like; and like other compounds.

In the thermal latent acid catalyst obtained by neutralizing theBronsted acid or the Lewis acid With the Lewis base, the ratio of thebasic activity of the Lewis base to the acidic activity of the acid ispreferably in the range from 0.1 to 10. When the ratio is less than 0.1,the catalytic activity of the acid may not be sufficiently suppressedduring storage and, when the ratio is more than 10, the catalyticactivity of the acid tends to be decreased. Thus, ratios outside of thespecified range are not advantageous.

The esters of sulfonic acids utilized as (C) the thermal latent acidcatalyst are compounds having the formula [4]: ##STR11## wherein R¹² isselected from the group consisting of phenyl group, substituted phenylgroup, naphthyl group, substituted naphthyl group and alkyl group andR¹³ is a group of 3 to 18 carbon atoms bonded with sulfonyloxy groupthrough a primary or secondary carbon atom which is selected from thegroup consisting of alkyl group, alkenyl group, aryl group, alkarylgroup, alkanol group, saturated or unsaturated cycloalkyl group andsaturated or unsaturated hydroxycycloalkyl group. Examples of the abovecompounds are esters of sulfonic acids, such as methane sulfonic acid,ethane sulfonic acid, benzene sulfonic acid, dodecylbenzene sulfonicacid, naphthalene sulfonic acid, nonylnaphthalene sulfonic acid andother like sulfonic acids, with primary alcohols, such as n-propanol,n-butanol, n-hexanol, n-octanol and the like, or secondary alcohols,such as isopropanol, 2-butanol, 2-hexanol, 2-octanol, cyclohexanol andthe like, and β-hydroxyalkylsulfonic esters prepared by the reaction ofthe sulfonic acids and compounds containing oxirane group.

The esters of phosphoric acid are, for example, compounds having theformula [5]: ##STR12## wherein R¹⁴ is a group of 3 to 10 carbon atomsselected from the group consisting of alkyl group, cycloalkyl group andaryl group and m is 1 or 2. Examples of the above compounds aremonoesters and diesters of phosphoric acid with primary alcohols, suchas n-propanol, n-butanol, n-hexanol, n-octanol, 2-ethylhexanol and thelike, or secondary alcohols, such as isopropanol, 2-butanol, 2-hexanol,2-octanol, cyclohexanol and the like, and β-hydroxyester compoundsobtained by reaction of phosphoric acid with oxirane compounds.

The onium compounds are compounds having one of the formulas [6] to [9]:

    [R.sup.15.sub.3 NR.sup.16 ].sup.+ X.sup.-                  [ 6]

    [R.sup.15.sub.3 PR.sup.16 ].sup.+ X.sup.-                  [ 7]

    [R.sup.15.sub.2 OR.sup.16 ].sup.+ X.sup.-                  [ 8]

and

    [R.sup.15.sub.2 SR.sup.16 ].sup.+ X.sup.-                  [ 9]

wherein R¹⁵ is a group of 1 to 12 carbon atoms selected from the groupconsisting of alkyl group, alkenyl group, aryl group, alkaryl group,alkanol group and cycloalkyl group, two R¹⁵ groups may be bondedtogether to form a heterocyclic ring in which N, P, O or S is the heteroatom, R¹⁶ is a hydrogen atom or a group of 1 to 12 carbon atoms selectedfrom the group consisting of alkyl group, alkenyl group, aryl group andalkaryl group and X- is selected from the group consisting of SbF₆ ⁻,AsF₆ ⁻, PF₆ ⁻ and BF₄ ⁻.

Among the thermal latent acid catalysts (C) utilized in thethermosetting composition of the invention, (F) the thermal latent acidcatalyst selected from the group consisting of a complex compound madefrom a Lewis acid and a Bronsted acid and a complex compound made from aLewis acid and a Bronsted salt is a novel thermal latent acid catalystparticularly effective for the thermosetting composition of theinvention and the complex compound made from a Lewis acid and a Bronstedacid is most excellent thermal latent acid catalyst.

The complex compound (F) is superior to other thermal latent acidcatalysts with respect to the storage stability, the reactivity of theheat curing and the property of the low temperature curing.

The Bronsted salt utilized for forming the complex compound (F) is acompound obtained by neutralizing the Bronsted acid described above witha base. Examples of the Bronsted salt are: compounds obtained byblocking Bronsted acids, such as sulfuric add, monoesters of sulfuricacid, phosphoric acid, monoesters and diesters of phosphoric acid,esters of polyphosphoric acid, monoesters and diesters of boric acid,sulfonic acid, carboxylic add, hologenocarboxylic acid and the like,with amines, such as ammonia, triethylamine, pyridine, aniline,morpholine, N-methylmorpholine, pyrrolidine, N-methylpyrrolidine,piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine,diethanolamine, triethanolamine, imidazole, N-methylimidazole and thelike, trialkylphosphines, such as tributylphosphine or the like,triarylphosphines, such as triphenylphosphine and the like; commercialacid-base blocked catalysts, such as Nacure 2500X®, Nacure 3525® andNacure 5225® (products of King Industry Co., Ltd.); and other likecompounds.

The novel thermal latent acid catalyst (F) is a complex compound formedby coordination of the conjugate base of the Br.0.nsted acid or theBronsted salt to the vacant orbital of the Lewis acid showing thecatalytic activity and can be obtained easily by mixing the Lewis aciddescribed above with the Br.0.nsted acid described above or with theBronsted salt described above in a mol ratio of the Br.0.nsted acid orthe Bronsted salt to the vacant orbital of the Lewis acid in the rangefrom 0.1 to 4. When the mol ratio is less than 0.1, the catalyticactivity of the Lewis acid is not always sufficiently suppressed duringstorage and, when the mol ratio is more than 4, the catalytic activityof the acid tends to be decreased.

In the thermosetting composition of the invention, the thermal latentacid catalysts (C) and (F) may be utilized singly or as a combination oftwo or more kinds. The amount utilized is usually in the range from 0.01to 10 weight parts, preferably in the range from 0.02 to 5 weight parts,based on 100 weight parts of the total solid component which is the sumof the compound (A) and the compound (B), the sum of the compound (D)and the optionally utilized compounds (A) and/or (B) or the sum of thecompound (A) and the compound (G).

Time and temperature required to cure the thermosetting composition ofthe invention is different depending on the temperature at which freecarboxyl group is regenerated from the blocked functional group of theformula [1] or the formula [3], kind of the reactive functional groupand the kind of the thermal latent acid catalyst. In general, curing iscompleted by heating at the temperature in the range from 50° to 200° C.for the time in the range from 2 minutes to 10 hours. The thermosettingcomposition of the invention has an advantageous property that it can becured at a temperature below 160° C. and higher temperatures are notnecessarily required.

The thermosetting composition of the invention can be utilized forcoating compositions, ink, adhesive, molded plastics and the likewithout other ingredients and, according to the needs, it may becompounded with coloring pigments, fillers, solvents, ultravioletadsorbents, antioxidants and other ingredients.

When the thermosetting composition of the invention is utilized as thetop coating material, it is realized by this method of coating thatlittle amount of organic solvents is discharged into air and excellentappearance is provided to the finished articles and the method can beadvantageously applied to the field of industrial coating such ascoating of automobiles.

When the thermosetting composition is utilized as the top coatingmaterial, it is preferred that the top coating material comprises 0 to100 weight parts, preferably 0 to 5 weight parts, of pigments based on100 weight parts of the thermosetting composition.

When the thermosetting composition of the invention is utilized forpreparing articles coated with plural of layers comprising a coloredbase coat and a clear coat, articles having very excellent finishedappearance can be obtained.

The base coat is made of a film forming composition comprising a resinbinder and pigments. As the resin binder, conventional acrylic polymers,polyesters including alkyd resins, polyurethanes and the like may beutilized as well as the thermosetting composition of the invention.

As the pigments comprised in the film forming composition for the basecoat, surface treated metallic pigments such as aluminum, copper, brass,bronze, stainless steel, iron oxides of mica form, metallic powders offlake form, mica coated with titanium oxide or iron oxide and the likemay be utilized. Inorganic pigments, such as titanium dioxide, ironoxides, yellow iron oxide, carbon black and the like, organic pigments,such as phthalocyanine blue, phthalocyanine green, quinacridone redpigments and the like, fillers, such as precipitated barium sulfate,clay, silica, tarc and the like, and other like pigments may also beutilized.

Conventionally utilized additives of various kinds, such as surfaceactive agents, levelling agents, rheology control agents, fillers,defoaming agents, organic cosolvents, catalysts and the like, may beadded to the film forming composition for the base coat.

Kind of the substrate to which the base coat is applied is notparticularly limited but various kinds of substrate materials, such aswoods, glasses, metals, fabrics, plastics, foamed articles, elastomersand the like, may be utilized.

Thickness of the base coat is not particularly limited but is generallyin the range from 5 to 40 μm and preferably in the range from 10 to 30μm.

The layer of the base coat is formed by application of the film formingcomposition for the base coat to the substrate, followed by removal oforganic solvent or water used as the solvent from the coating layer byheating or by simply standing.

The film forming composition for the clear coat is applied to the basecoat formed in the above. The film forming composition for the clearcoat is the themosetting composition of the invention.

Pigments, additives of various kinds, dyestuffs having goodweatherability and the like may be added to the film forming compositionfor the clear coat according to necessity within the range that theadditional ingredients do not affect adversely to the transparency ofthe clear coat.

Thickness of the clear coat is not particularly limited but generally inthe range from 20 to 100 μm and preferably in the range from 20 to 50μm.

As the method of application of the film forming composition for thebase coat and the film forming composition for the clear coat, generallyutilized methods, such as coating by brushes, spray coating, dipcoating, flow coating and the like, may be utilized. The preferablemethod among them is spray coating.

When the film forming composition for the base coat and the film formingcomposition for the clear coat have been applied to the substrate, thearticle is left standing for 1 to 20 minutes at the room temperature andthen baked for 2 minutes to 10 hours at 50° to 200° C. to obtain thecoated article of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention will be understood more readily with reference to thefollowing examples; however, these examples are intended to illustratethe invention and are not to be construed to limit the scope of theinvention.

Properties of the coated film were evaluated by the following methods.

(1) Acid Resistance 1

On a test piece, 2 ml of 40 weight % sulfuric acid was applied as spotsand condition of the coated film was observed by visual comparison afterstanding for 48 hour at 20° C.

(2) Acid Resistance 2

On a test piece, 2 ml of 40 weight % sulfuric acid was applied as spotsand condition of the coated film was observed by visual comparison afterheating for 30 minutes at 60° C.

(3) Acid Resistance 3

A test piece was dipped in 0.1N sulfuric acid and the condition ofcoated film was observed by visual comparison after standing for 24hours at 60° C.

(4) Impact Resistance

By using an impact tester (Japanese Industrial Standard K-5400 (1990),8.3.2, Du Pont method), a test piece was clamped to an impact frame of6.35 mm radius and a weight of 500 g was dropped from the height of 40cm on the test piece. Damage made on the coating film was observed byvisual comparison.

(5) Weathering Resistance

By using a sunshine weathermeter (Japanese Industrial Standard K-5400(1990) 9.8.1), a test piece was exposed for 1000 hours or 3000 hours and60 degree specular gloss (Japanese Industrial Standard K-5400 (1990) 7.660 degree specular gloss) of the coating film was measured. Condition ofthe coating film was observed by visual comparison or compared with thecondition before the exposure by using the measured values of gloss.

(6) Knoop Hardness

Measurement was made by using M type micro-hardnessmeter (manufacturedby Shimazu Seisakusho, Co., Ltd.) at 20° C. A larger value shows ahigher hardness.

(7) Non-volatile Matter

Non-volatile matter was measured by treating the sample in vacuo of 0.1mmHg at 50° C. for 3 hours.

(8) Gardener Viscosity

Gardener viscosity was measured by the method of Japanese IndustrialStandard K-5400 (1990) 4.5.1 (bubble tube viscometer).

Abbreviations and trade names used in the examples are listed in thefollowing.

AIBN: 2,2'-azo-bis-isobutyronitrile

TMSPMA: methacryloyloxypropyltrimethoxysilane

10% N-methylmorpholine: 10 weight % solution of N-methylmorpholine inxylene

10% PTSA: 10 weight % solution of p-toluene sulfonic acid in isopropylalcohol.

Acid catalyst A: a complex of zinc octanoate and triethylphosphatecontaining 12 weight % of zinc octanoate.

Acid catalyst B: 45 weight % solution in ethyl acetate ofN-methylmorpholine salt of dodecylbenzenesulfonic acid.

Chemitite MZ-11®: a product of Nippon Shokubai Kagaku Kogyo Co., Ltd.,2-(1-aziridinyl)ethyl methacrylate

Chemitite PZ-33®: a product of Nippon Shokubai Kagaku Kogyo Co., Ltd.,polyaziridine, content of aziridine 6.2 mol/kg.

Coronate EH®: a product of Nippon Polyurethane Kogyo Co., Ltd., trimerof hexamethylene diisocyanate, content of isocyanate 21 weight %.

CX-RS-1200®: a product of Nippon Shokubai Kagaku Kogyo Co., Ltd., apolyoxazoline compound, solid content 50%, glass transition temperature10° C., weight average molecular weight 18000 and oxazoline equivalentmolecular weight 555.

CX-RS-3200®: a product of Nippon Shokubai Kagaku Kogyo Co., Ltd., apolyoxazoline compound, solid content 50%, glass transition temperature10° C., weight average molecular weight 14000 and oxazoline equivalentmolecular weight 555.

Cymel 303®: a product of Mitsui Cyanamide Co., Ltd., methylated melamineresin, non-volatile matter 98 weight %.

Denacol EX-421®: a product of Nagase Kagaku Kogyo Co., Ltd., a polyepoxycompound, epoxy equivalent 155.

KR-214®: a product of Shinetsu Kagaku Kogyo Co., Ltd., silicone vanish,hydroxyl equivalent 490, non-volatile matter 70 weight %.

Modaflow®: a product of Monsanto Co., a leveling agent.

Titanium dioxide JR-602®: a product of Teikoku Kako Co., Ltd., titaniumdioxide of rutile type.

EXAMPLE OF PREPARATION OF MATERIAL 1 TO 3

Solutions of three kinds of the compound (A), A-1, A-2 and A-3, wereprepared.

(1) Preparation of α,β-unsaturated Compound

A mixture shown in Table 1 was charged into a four-necked flask which isequipped with a thermometer, a reflux condenser and a stirrer andstirred at 50° C. The reaction was finished when the acid value of themixture decreased to a value less than 30 and the reaction mixture wastransferred to a separating funnel after cooling by standing. Thereaction mixture was washed with 100 weight parts of alkaline watercontaining 10 weight % of sodium bicarbonate in a separation funnel andthen washed with 200 weight parts of deionized water repeatedly until pHof the washing water became below 7. The organic layer was dried byadding Molecular Sieve 4A1/16 (a product of Wako Junyaku Co., Ltd.) andstanding for 3 days at the room temperature. The α,β-unsaturatedcompounds obtained by this process, A-1(a), A-2(a) and A-3(a), containedeffective components in the amounts shown in Table 1. The contents ofthe effective components were determined by gas chromatography.

(2) Preparation of Solution of Compounds A-1, A-2 and A-3

Into a four-necked flask equipped with a thermometer, a refluxcondenser, a stirrer and a dropping funnel, an initial portion ofsolvent which was xylene was charged in an amount shown in Table 2,heated under stirring and kept at 80° C. A mixture of monomers and apolymerization initiator shown in Table 2 (`component of droppedmixture`) was added by dropping to the solvent at 80° C. at a constantrate for 2 hours. When the addition of the dropping component wasfinished, the mixture was kept at 80° C. for further 1 hour and, then,an additional amount of initiator solution shown in Table 2 (`additionalcatalyst`) was added to the mixture. The mixture was kept at 80° C. for4 hours before finishing the reaction and finally the compounds A-1, A-2and A-3 having the properties shown in Table 2 were obtained.

                  TABLE 1                                                         ______________________________________                                        Example of preparation of material                                                                1       2        3                                        ______________________________________                                        α,β-unsaturate compound                                                                A-1(a)  A-2(a)   A-3(a)                                   composition of material (weight part)                                         methacrylic acid    86.0    86.0     86.0                                     ethyl vinyl ether   86.5    --       --                                       isobutyl vinyl ether                                                                              --      120.2    --                                       3,4-dihydro-2H-pyran                                                                              --      --       100.9                                    hydroquinone monomethyl ether                                                                     0.2     0.2      0.2                                      35 weight % hydrochloric acid                                                                     0.1     0.1      0.1                                      content of the effective component                                                                94.5    95.3     95.1                                     (weight %)                                                                    ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Example of preparation of material                                                               1        2       3                                         ______________________________________                                        compound (A)       A-1      A-2     A-3                                       xylene (weight part)                                                                             200.0    200.0   200.0                                     composition of dropped mixture                                                (weight part)                                                                 α,β-unsaturated compound A-1(a)                                                       167.2    --      --                                        α,β-unsaturated compound A-2(a)                                                       --       195.2   --                                        α,β-unsaturated compound A-3(a)                                                       --       --      178.8                                     n-butyl methacrylate                                                                             100.0    100.0   100.0                                     methyl methacrylate                                                                              178.6    178.6   178.6                                     2-ethylhexyl acrylate                                                                            135.4    135.4   135.4                                     n-butyl acetate    135.9    106.8   123.8                                     AIBN               22.9     24.0    23.4                                      additional catalyst (weight part)                                             n-butyl acetate    57.0     57.0    57.0                                      AIBN               3.0      3.0     3.0                                       properties                                                                    non-volatile matter (weight %)                                                                   57.2     60.1    58.5                                      Gardener viscosity (25° C.)                                                               R-S      W-X     U                                         ______________________________________                                    

EXAMPLE OF PREPARATION OF MATERIAL 4

Solution of one kind of the compound (A), A-4, was prepared.

(1) Preparation of Polycarboxylic Acid A-4(a)

Into a four-necked flask equipped with a thermometer, a refluxcondenser, a stirrer and a dropping funnel, the following componentswere charged and the mixture was heated under stirring until thetemperature reached to 120° C.

    ______________________________________                                        pentaerythritol  136.0 weight parts                                           methyl isobutyl ketone                                                                         538.7 weight parts                                           ______________________________________                                    

To the mixture kept at 120° C., 672.0 weight parts ofmethylhexahydrophthalic anhydride was added by dropping for 2 hours andthe mixture was kept stirring under heating until acid value of themixture decreased to a value not more than 170. The acid value wasmeasured by diluting the sample 50 times by weight with a mixture ofpyridine and water (pyridine/water 9/1 by weight), heating for 30minutes at 90° C. and titrating with a standard solution of potassiumhydroxide. Thus, a solution of a tetrafunctional polycarboxy compoundA-4(a) was prepared.

(2) Preparation of Solution of Compound A-4

Into a flask of the same kind as the above, a mixture of the followingcomposition including the solution of the polycarboxyl compound preparedabove was charged and kept stirring at 50° C.

    ______________________________________                                        the solution of polycarboxyl compound of (1)                                                            336.7                                               isobutyl vinyl ether      120.2                                               hydrochloric acid, 35 weight %                                                                          0.2                                                 methyl isobutyl ketone    46.3                                                (quantity in weight parts)                                                    ______________________________________                                    

The reaction was finished when acid value of the mixture decreased to avalue not more than 12 and the mixture was transferred to a separationfunnel after cooling by standing. The reaction mixture was washed with100 weight parts of alkaline water containing 10 weight % of sodiumbicarbonate in the funnel and then washed with 300 weight parts ofdeionized water repeatedly until pH of the washing water became below 7.The organic layer was dried by adding Molecular Sieve 4A1/16 (a productof Wako Junyaku Co., Ltd.) and standing for 3 days at the roomtemperature. The solution of the compound A-4 thus prepared had 60.0weight % of non-volatile matter and Gardener viscosity of E-F at 25° C.

(3) Preparation of Solution of Compound A-5

Into a flask of the same kind as the above, a mixture of the followingcomposition including the solution of the polycarboxyl compound preparedabove was charged and kept stirring at 60° C.

    ______________________________________                                        the solution of polycarboxyl compound of (1)                                                            1277.5                                              n-propyl vinyl ether      447.9                                               2-ethylhexyl phosphate    0.8                                                 (quantity in weight parts)                                                    ______________________________________                                    

When the conversion obtained from the acid number reached 98% or more,the heating was stopped and excess amount of the vinyl ether and 348.2weight parts of methyl isobutyl ketone were removed by vacuumdistillation to obtain the solution of the compound A-5 containing 60weight % of the effective component and the Gardener viscosity of I at25° C.

EXAMPLE OF PREPARATION OF MATERIAL 5 AND 6

Solutions of two kinds of the compound (B), compounds B-1 and B-2, wereprepared by the following method.

Into a four-necked flask equipped with a thermometer, a refluxcondenser, a stirrer and a dropping funnel, 40.0 weight parts of solventwhich was xylene was charged, heated under stirring and kept at 100° C.A mixture of monomers and a polymerization initiator shown in Table 3(`component of dropped mixture`) was added by dropping to the solvent at100° C. at a constant rate for 2 hours. When the addition of thedropping component was finished, the mixture was kept at 100° C. forfurther 1 hour and, then, an additional amount of initiator solutionshown in Table 3 (`additional catalyst`) was added to the mixture. Themixture was kept at 100° C. for 2 hours before finishing the reactionand finally solutions of the compounds B-1 and B-2 having thecharacteristics shown in Table 3 were obtained.

                  TABLE 3                                                         ______________________________________                                        Example of preparation of material                                                                     5      6                                             ______________________________________                                        compound (A)             B-1    B-2                                           composition of dropped mixture (weight part)                                  glycidyl methacrylate    28.40  --                                            TMSPMA                   --     16.60                                         MZ-11                    --     --                                            n-butyl methacrylate     20.00  20.00                                         methyl methacrylate      27.70  51.19                                         2-ethylhexyl acrylate    23.90  12.21                                         n-butyl acetate          54.00  54.00                                         AIBN                     2.00   2.00                                          additional catalyst (weight part)                                             n-butyl acetate          3.80   3.80                                          AIBN                     0.20   0.20                                          properties                                                                    non-volatile matter (weight %)                                                                         50.8   50.5                                          Gardener viscosity       S      P-Q                                           ______________________________________                                    

EXAMPLE OF PREPARATION OF MATERIAL 7 AND 8

Solutions of two kinds of compound (D), compounds D-1 and D-2, wereprepared by the following method.

Into a four-necked flask equipped with a thermometer, a refluxcondenser, a stirrer and a dropping funnel, an initial portion ofsolvent which was xylene was charged in an amount shown in Table 4,heated under stirring and kept at 80° C. A mixture of monomers and apolymerization initiator shown in Table 4 (`component of droppedmixture`) was added by dropping to the solvent at 80° C. at a constantrate for 2 hours. When the addition of the dropping component wasfinished, the mixture was kept at 80° C. for further 1 hour and, then,an additional amount of initiator solution shown in Table 4 (`additionalcatalyst`) was added to the mixture. The mixture was kept at 80° C. for4 hours before finishing the reaction and finally solutions of thecompounds D-1 and D-2 having the properties shown in Table 4 wereobtained.

                  TABLE 4                                                         ______________________________________                                        Example of preparation of material                                                                     7      7                                             ______________________________________                                        compound (D)             D-1    D-2                                           xylene                   40.0   40.0                                          composition of dropped mixture (weight part)                                  α,β-unsaturated compound A-3(a)                                                             36.0   --                                            α,β-unsaturated compound A-2(a)                                                             --     19.5                                          glycidyl methacrylate    14.2   --                                            2-hydroxyethyl methacrylate                                                                            --     32.5                                          n-butyl methacrylate     20.0   20.0                                          methyl methacrylate      18.5   18.8                                          2-ethylhexyl acrylate    13.5   20.1                                          TMSPMA                   16.6   --                                            n-butyl acetate          28.7   36.6                                          AIBN                     4.5    4.5                                           additional catalyst (weight part)                                             n-butyl acetate          7.6    7.6                                           AIBN                     0.4    0.4                                           properties                                                                    non-volatile matter (weight %)                                                                         58.5   55.3                                          Gardener viscosity (25° C.)                                                                     V-W    Y-Z                                           ______________________________________                                    

EXAMPLES 1 TO 11

These examples show application of the composition to one coat solidcolor coating.

(1) Preparation of Coating Compositions

Components summarized in Table 5 were utilized for the preparation ofthe coating compositions. A part of or all materials were charged into asand mill and dispersed until the particle size decreased to not morethan 10 μm. Materials excluding following components were charged intothe sand mill: Denacol EX-421 in Example 1, the compound B-2 in Example2, Chemitite PZ-33 in Example 3, the compound A-4 in Example 4, CoronateEH in Example 5, Cymel 303 in Example 6, the compound B-1 in Example 7,KR-214 in Example 8, the compound B-7 in Example 9 and Cymel 303 inExample 11. All the raw materials were charged into the sand mill inExample 10. In Examples 1 through 9 and Example 11, one componentcoating compositions were prepared by adding the materials which werenot treated by the sand mill to the materials treated by the sand mill.In Example 10, the materials treated by the sand mill were utilized forthe preparation of one component coating compositions. The coatingcompositions prepared were diluted by a mixture of xylene and butylacetate to the viscosity of 1 poise (measured by Brookfield typeviscometer at 20° C.) and, after adding deionized water to make thewater concentration of 0.3 weight %, stored in a sealed condition at 30°C. After the coating compositions were stored for 30 days at 30° C.,viscosity was measured. The results summarized in Table 6 show that theincrease of viscosity was very slight in all cases and that the coatingcompositions had excellent storage stability even though a considerableamount of water was present.

(2) Preparation of Test Piece

Cationic electrodeposit paint AQUA No.4200® (a product of NOFCORPORATION) was applied by electrodeposition to a soft steel platetreated with zinc phosphate in an amount to form a film having driedthickness of 20 μm and the coated plate was baked at 175° C. for 25minutes. Intermediate coating paint EPICO No.1500CP Sealer® (a productof NOF CORPORATION) was applied to the prepared plate by air spraying inan amount to form a film having dried thickness of 40 μm and the platewas baked at 140° C. for 30 minutes to obtain a base test piece.

The raw coating compositions prepared in (1) were diluted with thinner(a mixture of xylene and butyl acetate in 8 to 2 ratio) to a viscosityrequired for spraying (25 seconds at 20° C. by Ford cup No. 4) andapplied to the base test piece prepared before by air spray coating.Test pieces were prepared by curing the coated pieces in the conditionsshown in Table 6.

Results of the evaluation of coatings are shown in Table 6. In allcases, uniform coating having good gloss were prepared. All the coatingsshowed excellent acid resistance, impact resistance, weatheringresistance and hardness when they were cured at 140° C.

Weathering resistance was evaluated by exposure for 1000 hours.

                                      TABLE 5                                     __________________________________________________________________________    (Part 1)                                                                      Example          1   2   3   4   5   6                                        __________________________________________________________________________    compounding recipe in weight parts                                            compound A-1     100 --  --  --  100 --                                       compound A-2     --  100 --  --  --  100                                      compound A-3     --  --  100 --  --  --                                       compound A-4     --  --  --  50.0                                                                              --  --                                       compound B-1     --  --  --  100 --  --                                       compound B-2     --  100 --  --  --  --                                       compound B-7     --  --  --  --  --  --                                       compound D-1     --  --  --  --  --  --                                       compound D-2     --  --  --  --  --  --                                       EX-421           15.5                                                                              --  --  --  --  --                                       PZ-33            --  --  16.1                                                                              --  --  --                                       Coronate EH      --  --  --  --  20.0                                                                              --                                       Cymel 303        --  --  --  --  --  14.0                                     KR-214           --  --  --  --  --  --                                       titanium dioxide 52.4                                                                              80.0                                                                              52.9                                                                              56.0                                                                              56.0                                                                              51.2                                     Modaflow         0.3 0.5 0.3 0.3 0.3 0.3                                      10% PTSA         --  --  --  --  --  1.9                                      10% N-methyl-    --  --  --  --  --  1.2                                      morpholine                                                                    xylene           7   14  3   8   4   5                                        n-butyl acetate  2   4   2   3   2   2                                        the compound (E)                                                              n-propyl vinyl ether                                                                           3.6 6.1 7.3 --  --  --                                       isobutyl vinyl ether                                                                           --  --  --  6.7 5.6 --                                       3,4-dihydro-2H-pyran                                                                           --  --  --  --  --  5.4                                      __________________________________________________________________________    (Part 2)                                                                      Example          7     8   9   10    11                                       __________________________________________________________________________    compounding recipe in weight parts                                            compound A-1     --    --  --  --    --                                       compound A-2     --    --  --  --    --                                       compound A-3     100   100 100 --    --                                       compound A-4     --    --  --  --    --                                       compound B-1     100   --  --  --    --                                       compound B-2     --    --  --  --    --                                       compound B-7     --    --  10.9                                                                              --    --                                       compound D-1     --    --  --  100   --                                       compound D-2     --    --  --  --    100                                      EX-421           --    --  --  --    --                                       PZ-33            --    --  --  --    --                                       Coronate EH      --    --  --  --    --                                       Cymel 303        --    --  --  --    10.5                                     ICR-214          --    49.0                                                                              --  --    --                                       titanium dioxide 80.0  67.4                                                                              48.7                                                                              40.0  48.4                                     Modaflow         0.5   0.3 0.3 0.3   0.3                                      10% PTSA         --    --  1.8 --    1.8                                      10% N-methyl-    --    --  1.2 --    1.2                                      morpholine                                                                    xylene           5     15  8   2     1                                        n-butyl acetate  4     3   2   3     2                                        the compound (E)                                                              n-propyl vinyl ether                                                                           15.2  11.6                                                                              2.0 --    --                                       isobutyl vinyl ether                                                                           --    --  --  7.6   --                                       3,4-dihydro-2H-pyran                                                                           --    --  --  --    8.7                                      __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    (Part 1)                                                                      Example  1        2          3                                                __________________________________________________________________________    compound (A)                                                                           A-1      A-2        A-3                                              compound (B)                                                                           EX-421   B-2        PZ-33                                                     epoxy group                                                                            alkoxysilane group                                                                       imino group                                      compound (D)                                                                           --       --         --                                               ratio of                                                                      mixing solid                                                                  components                                                                    (A)      78.7     54.3       78.4                                             (B)      21.3     45.7       21.6                                             (D)      --       --         --                                               storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                      1.0      1.0        1.0                                              (poise)                                                                       viscosity after                                                                        2.5      3.0        4.0                                              30 days (poise)                                                               curing condition                                                                       120° C.                                                                    140° C.                                                                     120° C.                                                                     140° C.                                                                      120° C.                                                                    140° C.                                        30 min                                                                            30 min                                                                             30 min                                                                             30 min                                                                              30 min                                                                            30 min                                       properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                      good                                                                              good good good  good                                                                              good                                         acid resistance 2                                                                      stain                                                                             good stain                                                                              good  stain                                                                             good                                         acid resistance 3                                                                      good                                                                              good good good  cloud                                                                             good                                         impact resistance                                                                      good                                                                              good good good  good                                                                              good                                         weathering                                                                             83% 87%  90%  94%   81% 85%                                          resistance                                                                    Knoop hardness                                                                         8.8 10.8 10.0 11.0  9.1 10.5                                         __________________________________________________________________________    (Part 2)                                                                      Example  4        5          6                                                __________________________________________________________________________    compound (A)                                                                           A-4      A-1        A-2                                              compound (B)                                                                           B-1      Coronate EH                                                                              Cymel 303                                                 epoxy group                                                                            isocyanate alkylated                                                          group      aminomethylol                                                                 group                                            compound (D)                                                                           --       --         --                                               ratio of                                                                      mixing solid                                                                  components                                                                    (A)      37.1     74.1       81.1                                             (B)      62.9     25.9       18.9                                             (D)      --       --         --                                               storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                      1.0      1.0        1.0                                              (poise)                                                                       viscosity after                                                                        2.8      3.0        2.5                                              30 days (poise)                                                               curing condition                                                                       120° C.                                                                    140° C.                                                                     120° C.                                                                     140° C.                                                                      120° C.                                                                    140° C.                                        30 min                                                                            30 min                                                                             30 min                                                                             30 min                                                                              30 min                                                                            30 min                                       properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                      good                                                                              good good good  good                                                                              good                                         acid resistance 2                                                                      stain                                                                             good stain                                                                              good  good                                                                              good                                         acid resistance 3                                                                      good                                                                              good good good  good                                                                              good                                         impact resistance                                                                      good                                                                              good good good  good                                                                              good                                         weathering                                                                             83% 86%  84%  87%   82% 86%                                          resistance                                                                    Knoop hardness                                                                         7.7 9.9  9.5  11.2  10.0                                                                              10.7                                         __________________________________________________________________________    (Part 3)                                                                      Example  7         8         9                                                __________________________________________________________________________    compound (A)                                                                           A-3      A-3        A-3                                              compound (B)                                                                           B-1      KR-214     B-7                                                       epoxy group                                                                            silanol group                                                                            acetal group                                     compound (D)                                                                           --       --         --                                               ratio of                                                                      mixing solid                                                                  components                                                                    (A)      53.5     63.0       84.3                                             (B)      46.5     37.0       15.7                                             (D)      --       --         --                                               storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                      1.0      1.0        1.0                                              (poise)                                                                       viscosity after                                                                        2.6      3.5        2.8                                              30 days (poise)                                                               curing condition                                                                       120° C.                                                                    140° C.                                                                     120° C.                                                                     140° C.                                                                      120° C.                                                                    140° C.                                        30 min                                                                            30 min                                                                             30 min                                                                             30 min                                                                              30 min                                                                            30 min                                       properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                      good                                                                              good good good  good                                                                              good                                         acid resistance 2                                                                      stain                                                                             good stain                                                                              good  good                                                                              good                                         acid resistance 3                                                                      good                                                                              good cloud                                                                              good  good                                                                              good                                         impact resistance                                                                      good                                                                              good good good  good                                                                              good                                         weathering                                                                             81% 85%  88%  93%   84% 88%                                          resistance                                                                    Knoop hardness                                                                         8.2 10.4 8.7  10.5  10.7                                                                              11.1                                         __________________________________________________________________________    (Part 4)                                                                      Example   10           11                                                     __________________________________________________________________________    compound (A)                                                                            --           --                                                     compound (B)                                                                            --           Cymel 303                                                                     alkylated amino-                                                              methylol group                                         compound (D)                                                                            D-1          D-2                                                              epoxy group  hydroxyl group                                                   alkoxysilane group                                                  ratio of                                                                      mixing solid                                                                  components                                                                    (A)       --           --                                                     (B)       --           16.0                                                   (D)       100          84.0                                                   storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                       1.0          1.0                                                    (poise)                                                                       viscosity after                                                                         3.0          3.2                                                    30 days (poise)                                                               curing condition                                                                        120° C.                                                                     140° C.                                                                        120° C.                                                                     140° C.                                              30 min                                                                             30 min  30 min                                                                             30 min                                            properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                       good good    good good                                              acid resistance 2                                                                       stain                                                                              good    good good                                              acid resistance 3                                                                       good good    good good                                              impact resistance                                                                       good good    good good                                              weathering                                                                              82%  87%     81%  85%                                               resistance                                                                    Knoop hardness                                                                          9.5  11.3    10.2 10.8                                              __________________________________________________________________________     .sup.1) good: no change was observed.                                         stain: slight stain was observed                                              cloud: surface was slightly cloudy                                       

COMPARATIVE EXAMPLES 1 TO 11

The components for Examples 1 to 11 listed in Table 5 were used forComparative examples 1 to 11 respectively except that the compound (E)was not used and coating compositions were prepared by the same methodas in Examples 1 to 11. Change of viscosity caused by the absence of thecompound (E) was compensated by using xylene.

The coating compositions thus prepared were evaluated on the storagestability by the same method as in Examples 1 to 11. In Comparativeexamples 1 to 11, viscosity increased remarkably with the period ofstorage, leading finally to gellation after 20 days because carboxylgroups were activated by the presence of a considerable amount of waterand the compositions did not comprise the compound (E) to block thecarboxyl group again.

EXAMPLES 12 TO 17

These examples show application of the composition to two coat one bakemetallic color coating.

(1) Preparation of Clear Coating

One component clear coating compositions were prepared by mixing rawmaterials shown in Table 7. The clear coating compositions prepared wereevaluated on storage stability by the same method as in Example 1 to 11.Increase of viscosity was very slight in all cases tested and thecoating compositions were shown to have excellent storage stability asshown in Table 8 even though a considerable amount of water was present.

2) Preparation of Test Piece

Raw coating compositions thus prepared were diluted by the same methodas in Examples 1 to 11. Base test pieces were also prepared by the samemethod as in Examples 1 to 11. A silver metallic base coatingcomposition, BELCOAT No.6000® (a product of NOF CORPORATION) was appliedto the base test piece by air spraying with interval of 1 minute 30seconds in 2 stages in an amount to form a film having dried thicknessof 15 μm. After the test pieces were set at 20° C. for 3 minutes, thediluted raw clear coating compositions were coated by air spray coatingand the test pieces were cured in the condition shown in Table 8 toprepare final test pieces.

Results of the evaluation listed in Table 8 show that, in all cases,uniform coatings having good gloss were prepared and the coating showedexcellent acid resistance, impact resistance, weathering resistance andhardness when they were cured at 140° C.

Weathering resistance was evaluated by the same method as in Table 6.

                                      TABLE 7                                     __________________________________________________________________________    Example          12  13  14  15  16  17                                       __________________________________________________________________________    compounding recipe in weight parts                                            compound A-2     100 --  --  --  --  --                                       compound A-4     --  50  --  --  --  50                                       compound A-5     --  --  --  --  29.4                                                                              --                                       compound B-1     --  100 --  --  --  100                                      compound B-2     100 --  --  --  --  --                                       compound D-1     --  --  100 --  --  --                                       compound D-2     --  --  --  100 --  --                                       Cymel 303        --  --  --  10.5                                                                              --  --                                       CX-RS-3200       --  --  --  --  100 --                                       Modaflow         0.2 0.1 0.1 0.1 0.1 --                                       10% PTSA         --  --  --  1.8 1.8 --                                       10% N-methyl-    --  --  --  1.1 1.1 --                                       morpholine                                                                    zinc octanoate   --  --  --  --  --  2.5                                      triethyl phosphate                                                                             --  --  --  --  --  18.3                                     xylene           5   4   3   3   3   2                                        n-butyl acetate  1   1   1   1   1   1                                        the compound (E)                                                              n-propyl vinyl ether                                                                           4.2 --  --  --  --  --                                       isobutyl vinyl ether                                                                           --  2.5 6.0 2.2 2.6 3.2                                      __________________________________________________________________________

                  TABLE 8                                                         ______________________________________                                        (Part 1)                                                                      Example    12             13                                                  ______________________________________                                        compound (A)                                                                             A-2            A-4                                                 compound (B)                                                                             B-2            B-1                                                            alkoxysilane group                                                                           epoxy group                                         compound (D)                                                                             --             --                                                  ratio of                                                                      mixing solid                                                                  components                                                                    (A)        54.3           37.1                                                (B)        45.7           62.9                                                (D)        --             --                                                  storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                        1.0            1.0                                                 (poise)                                                                       viscosity after                                                                          1.2            1.2                                                 30 days (poise)                                                               curing condition                                                                         120° C.                                                                         140° C.                                                                          120° C.                                                                       140° C.                                      30 min   30 min    30 min 30 min                                   properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                        good     good      good   good                                     acid resistance 2                                                                        stain    good      stain  good                                     acid resistance 3                                                                        cloud    good      good   good                                     impact resistance                                                                        good     good      good   good                                     weathering good     good      good   good                                     resistance                                                                    Knoop hardness                                                                           8.8      10.9      9.0    11.2                                     ______________________________________                                        (Part 2)                                                                      Example    14             15                                                  ______________________________________                                        compound (A)                                                                             --             --                                                  compound (B)                                                                             --             Cymel 303                                                                     alkylated amino-                                                              methylol group                                      compound (D)                                                                             D-1            D-2                                                            epoxy group    hydroxyl group                                                 alkoxysilane group                                                 ratio of                                                                      mixing solid                                                                  components                                                                    (A)         --            --                                                  (B)        --             16.0                                                (D)        100            84.0                                                storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                        1.0            1.0                                                 (poise)                                                                       viscosity after                                                                          1.2            1.2                                                 30 days (poise)                                                               curing condition                                                                         120° C.                                                                         140° C.                                                                          120° C.                                                                       140° C.                                      30 min   30 min    30 min 30 min                                   properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                        good     good      good   good                                     acid resistance 2                                                                        stain    good      good   good                                     acid resistance 3                                                                        good     good      good   good                                     impact resistance                                                                        good     good      good   good                                     weathering good     good      good   good                                     resistance                                                                    Knoop hardness                                                                           8.1      10.3      10.8   11.5                                     ______________________________________                                        (Part 3)                                                                      Example    16             17                                                  ______________________________________                                        compound (A)                                                                             A-5            A-4                                                 compound (B)                                                                             CX-RS-3200     B-1                                                            oxazoline group                                                                              epoxy group                                         compound (D)                                                                             --             --                                                  ratio of                                                                      mixing solid                                                                  components                                                                    (A)        29.4           37.1                                                (B)        70.6           62.9                                                (D)        --             --                                                  storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                        1.0            1.0                                                 (poise)                                                                       viscosity after                                                                          1.2            1.3                                                 30 days (poise)                                                               curing condition                                                                         120° C.                                                                         140° C.                                                                          120°  C.                                                                      140° C.                                      30 min   30 min    30 min 30 min                                   properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                        good     good      good   good                                     acid resistance 2                                                                        good     good      good   good                                     acid resistance 3                                                                        good     good      good   good                                     impact resistance                                                                        good     good      good   good                                     weathering good     good      good   good                                     resistance                                                                    Knoop hardness                                                                           9.5      11.9      11.0   12.3                                     ______________________________________                                         .sup.1) good: No change was observed.                                         stain: slight stain was observed                                              cloud: surface was slightly cloudy                                       

COMPARATIVE EXAMPLES 12 TO 17

The components for Examples 12 to 17 listed in Table 7 were used forComparative examples 12 to 17 respectively except that the compound (E)was not used and coating compositions were prepared by the same methodas in Examples 12 to 17. Change of viscosity caused by the absence ofthe compound (E) was compensated by using xylene.

The coating compositions thus prepared were evaluated on the storagestability by the same method as in Examples 12 to 17. In Comparativeexamples 12 to 17, viscosity increased remarkably with the period ofstorage, leading finally to gellation after 20 days because carboxylgroups were activated by the presence of a considerable amount of waterand the compositions did not comprise the compound (E) to block thecarboxyl group again.

EXAMPLES 18 TO 21

Four kinds of thermal latent acid catalysts F-1 to F-4 were prepared bythe following method.

Into test tubes, 50.0 weight parts each of a mixed solvent of methylisobutyl ketone and ethyl acetate in 1/1 weight ratio were charged andcomponents for the thermal latent acid catalysts shown in Table 9 wereadded to the solutions under stirring.

The test tubes were left standing for 3 hours and 50 weight % solutionsof thermal latent acid catalysts F-1 to F-4 were obtained.

                  TABLE 9                                                         ______________________________________                                        Example            18      19     20    21                                    ______________________________________                                        thermal latent acid catalyst                                                                     F-1     F-2    F-3   F-4                                   compounding recipe in weight parts                                            Lewis acid                                                                    zinc octanoate     20.1    --     --    32.1                                  dibutyltin dilaurate                                                                             --      34.8   --    --                                    tin octanoate      --      --     22.4  --                                    Bronsted                                                                      acid salt                                                                     acid                                                                          di(2-ethylhexyl)-  24.1    --     23.3  --                                    sulfosuccinic acid                                                            (2-ethylhexyl)     --      9.7    --    --                                    phosphate                                                                     monochloroacetic   --      --     --    8.7                                   acid                                                                          base                                                                          N-methylmorpholine 5.8     5.5    --    --                                    pyridine           --      --     4.3   --                                    triethylamine      --      --     --    9.2                                   solvent                                                                       methyl isobutyl    25.0    25.0   25.0  25.0                                  ketone                                                                        ethyl acetate      25.0    25.0   25.0  25.0                                  ______________________________________                                    

EXAMPLES 22 TO 26

These examples show application of the composition to one coat solidcolor coating.

(1) Preparation of Coating Material

Components summarized in Table 10 were utilized for the preparation ofthe coating materials. A part of or all materials were charged into asand mill and dispersed until the particle size decreased to not morethan 10 μm. Materials excluding following components were charged intothe sand mill: Denacol EX-421 in Example 22, the compound B-2 in Example23, the compound B-1 in Example 24 and the compound A-4 in Example 25.All the raw materials were charged into the sand mill in Example 26. InExamples 22 to 25, one component coating compositions were prepared byadding the materials which were not treated by the sand mill to thematerials treated by the sand mill. In Example 26, the materials treatedby the sand mill were utilized for the preparation of one componentcoating composition. The coating compositions prepared were diluted withthinner (a mixture of xylene and butyl acetate in 8 to 2 weight ratio)to the viscosity of 1 poise (measured by Brookfield type viscometer at20° C.) and stored in a sealed condition at 50° C. After the coatingcompositions were stored for 30 days at 50° C., viscosity was measured.The results summarized in Table 11 show that the increase of viscositywas very slight in all cases and that the coating materials hadexcellent storage stability.

(2) Preparation of Test Piece

Cationic electrodeposit paint AQUA No.4200® (a product of NOFCORPORATION) was applied by electrodeposition to a soft steel platetreated with zinc phosphate in an amount to form a film having driedthickness of 20 μm and the coated plate was baked at 175° C. for 25minutes. Intermediate coating paint EPICO No.1500CP Sealer® (a productof NOF CORPORATION, Ltd.) was applied to the prepared plate by airspraying in an amount to form a film having dried thickness of 40 μm andthe plate was baked at 140° C. for 30 minutes to obtain a base testpiece.

The raw coating materials prepared in (1) were diluted with thinner (amixture of xylene and butyl acetate in 8 to 2 ratio) to a viscosityrequired for spraying (25 seconds at 20° C. by Ford cup No. 4) andapplied to the base test piece prepared before by air spray coating.Test pieces were prepared by curing the coated pieces in the conditionsshown in Table 11.

Results of the evaluation of coatings are shown in Table 11. In allcases, uniform coating having good gloss were prepared. All the coatingsshowed excellent acid resistance, impact resistance, weatheringresistance and hardness.

Weathering resistance was evaluated by the same method as in Table 6.

                                      TABLE 10                                    __________________________________________________________________________    Example          22  23  24  25  26                                           __________________________________________________________________________    compounding recipe in weight parts                                            compound A-1     100 --  --  --  --                                           compound A-2     --  100 --  --  --                                           compound A-3     --  --  100 --  --                                           compound A-4     --  --  --  50.0                                                                              --                                           compound B-2     --  100 --  --  --                                           compound B-1     --  --  100 100 --                                           compound D-1     --  --  --  --  100                                          EX-421           15.5                                                                              --  --  --  --                                           titanium dioxide 52.4                                                                              80.0                                                                              80.0                                                                              56.0                                                                              40.0                                         Modaflow         0.3 0.5 0.5 0.3 0.3                                          acid catalyst F-1                                                                              3.9 --  --  4.3 --                                           acid catalyst F-2                                                                              --  6.2 --  --  --                                           acid catalyst F-3                                                                              --  --  --  --  3.3                                          acid catalyst F-4                                                                              --  --  3.7 --  --                                           xylene           8.0 14.0                                                                              16.0                                                                              12.0                                                                              8.0                                          n-butyl acetate  2.0 3.5 4.0 3.0 2.0                                          __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________    (Part 1)                                                                      Example        22       23        24                                          __________________________________________________________________________    compound (A)   A-1      A-2       A-3                                         compound (B)   EX-421   B-1       B-2                                                        epoxy group                                                                            alkoxysilane group                                                                      epoxy group                                 compound (D)   --       --        --                                          acid catalyst (F)                                                                            F-1      F-2       F-4                                         ratio of                                                                      mixing solid                                                                  components                                                                    (A)            78.7     54.3      53.5                                        (B)            21.3     45.7      46.5                                        (D)            --       --        --                                          content of (F) (weight %)                                                                    2.68     2.80      1.69                                        100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0      1.0       1.0                                         (poise)                                                                       viscosity after                                                                              1.2      1.3       1.2                                         30 days (poise)                                                               curing condition                                                                             120° C. × 30 min                                                          120° C. × 30 min                                                           120° C. × 30 min               properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good     good      good                                        acid resistance 2                                                                            good     good      good                                        acid resistance 3                                                                            good     good      good                                        impact resistance                                                                            good     good      good                                        weathering     83%      90%       85%                                         resistance                                                                    Knoop hardness 10.9     11.8      11.6                                        __________________________________________________________________________    (Part 2)                                                                      Example           25       26                                                 __________________________________________________________________________    compound (A)      A-4      --                                                 compound (B)      B-2      --                                                                   epoxy group                                                 compound (D)      --       D-1                                                                           epoxy group                                                                   alkoxysilane group                                 acid catalyst (F) F-1      F-3                                                ratio of                                                                      mixing solid                                                                  components                                                                    (A)               37.1     --                                                 (B)               62.9     --                                                 (D)               --       100                                                content of (F) (weight %)                                                                       2.66     2.82                                               100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity 1.0      1.0                                                (poise)                                                                       viscosity after   1.2      1.3                                                30 days (poise)                                                               curing condition  120° C. × 30 min                                                          120° C. × 30 min                      properties of                                                                 coating.sup.1)                                                                acid resistance 1 good     good                                               acid resistance 2 good     good                                               acid resistance 3 good     good                                               impact resistance good     good                                               weathering        86%      87%                                                resistance                                                                    Knoop hardness    12.1     12.0                                               __________________________________________________________________________     .sup.1) good: no change was observed.                                    

COMPARATIVE EXAMPLES 18 AND 19

Components listed in Table 12 were utilized for the preparation of thecoating compositions. The components were dispersed and made intocoating compositions by the same method as in Examples 22 to 26. Thematerials excluding polycarboxylic acid of Example of preparation ofmaterial A-4 (a) in Comparative example 18 and excluding the compoundA-4 in Comparative example 19 were dispersed by using a sand mill andutilized for preparation of coating compositions.

The coating materials thus prepared were evaluated on the storagestability by the same method as in Examples 22 to 26. As shown in Table13, in Comparative example 18, viscosity increased remarkably with theperiod of storage, leading finally to gellation after 5 days, becauseneither carboxyl group or epoxy group was blocked to preventcrosslinking reaction of the both functional groups under the storagecondition.

Weathering resistance was evaluated by the same method as in Table 6.

                  TABLE 12                                                        ______________________________________                                        Comparative example   18      19                                              ______________________________________                                        compounding recipe in weight parts                                            polycarboxylic acid A-4 (a)                                                                         33.3    --                                              compound A-4          --      50.0                                            compound B-1          100     100                                             titanium dioxide JR-602                                                                             56.0    56.0                                            Modaflow              0.3     0.3                                             catalyst F-1          3.8     --                                              zinc octanoate        --      0.9                                             xylene                8.0     12.0                                            n-butyl acetate       2.0     3.0                                             ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        Comparative example                                                                          18           19                                                ______________________________________                                        compound (A)   polycarboxylic                                                                             A-4                                                              acid A-4 (a)                                                   compound (B)   B-1          B-1                                                              epoxy group  epoxy group                                       acid catalyst (F)                                                                            F-1          zinc octanoate                                    ratio of                                                                      mixing solid                                                                  components                                                                    (A)            28.6         37.1                                              (B)            71.4         62.9                                              content of (F) (weight %)                                                                    2.68         1.11                                              100 × (F)/{(A) + (B)}                                                   storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0          1.0                                               (poise)                                                                       viscosity after                                                                              gel after 5 days                                                                           gel after 2 days                                  30 days (poise)                                                               curing condition                                                                             120° C. × 30 min                                                              120° C. × 30 min                     properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good         good                                              acid resistance 2                                                                            good         good                                              acid resistance 3                                                                            good         good                                              impact resistance                                                                            good         good                                              weathering     87%          89%                                               resistance                                                                    Knoop hardness 12.0         12.4                                              ______________________________________                                         .sup.1) good: no change was observed.                                    

EXAMPLES 27 TO 29

These examples show application of the composition to two coat one bakemetallic color coating.

(1) Preparation of Clear Coating Compositions

One component clear coating compositions were prepared by mixing rawmaterials shown in Table 14. The clear coating compositions preparedwere evaluated on storage stability by the same method as in Example 22to 26. As shown in Table 15, increase of viscosity was very slight inall cases tested and coating materials were shown to have excellentstorage stability.

2) Preparation of Test Pieces

Raw coating materials thus prepared were diluted by the same method asin Examples 22 to 26. Base test pieces were also prepared by the saμmemethod as in Examples 22 through 26. A silver metallic base coatingcomposition BELCOAT No.6000® (a product of NOF CORPORATION) was appliedto the base test piece by air spraying with interval of 1 minute 30seconds in 2 stages in an amount to form a film having dried thicknessof 15 μm. After the test piece was set at 20° C. for 3 minutes, thediluted raw clear coating compositions were coated by air spray coatingand the test pieces were cured in the condition shown in Table 15 toprepare final test pieces.

Results of evaluation listed in Table 15 show that, in all cases,uniform coating films having good gloss were prepared and the coatingshowed excellent acid resistance, impact resistance, weatheringresistance and hardness.

Weathering resistance was evaluated by the same method as in Table 6.

                  TABLE 14                                                        ______________________________________                                        Example            27       28      29                                        ______________________________________                                        compounding recipe in weight parts                                            compound A-2       33.3     --      --                                        compound A-4       --       50.0    --                                        compound B-2       100      --      --                                        compound B-1       --       100     --                                        compound D-1       --       --      100                                       Modaflow           0.2      0.1     0.1                                       catalyst F-1       --       4.3     --                                        catalyst F-2       6.2      --      --                                        catalyst F-3       --       --      3.3                                       xylene             3.5      3.0     2.0                                       n-butyl acetate    0.9      0.8     0.5                                       ______________________________________                                    

                                      TABLE 15                                    __________________________________________________________________________    Example        27        28       29                                          __________________________________________________________________________    compound (A)   A-2       A-4      --                                          compound (B)   B-2       B-1      --                                                         alkoxysilane group                                                                      epoxy group                                          compound (D)   --        --       D-1                                                                           epoxy group                                                                   alkoxysilane group                          acid catalyst (F)                                                                            F-2       F-1      F-3                                         ratio of                                                                      mixing solid                                                                  components                                                                    (A)            54.3      37.1     --                                          (B)            45.7      62.9     --                                          (D)            --        --       100                                         content of (F) (weight %)                                                                    2.80      2.66     2.82                                        100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0       1.0      1.0                                         (poise)                                                                       viscosity after                                                                              1.3       1.2      1.3                                         30 days (poise)                                                               curing condition                                                                             120° C. × 30 min                                                           120° C. × 30 min                                                          120° C. × 30 min               properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good      good     good                                        acid resistance 2                                                                            good      good     good                                        acid resistance 3                                                                            good      good     good                                        impact resistance                                                                            good      good     good                                        weathering     good      good     good                                        resistance                                                                    Knoop hardness 10.9      11.3     11.1                                        __________________________________________________________________________     .sup.1) good: no change was observed.                                    

COMPARATIVE EXAMPLES 20 AND 21

Clear coating materials were prepared by using materials of thecompositions shown in Table 16 and evaluated on storage stability by thesame method as in Examples 22 to 26.

In Comparative example 20, as shown in Table 17, viscosity increasedremarkably with the period of storage, leading finally to gellationafter 5 days, because neither carboxyl group or epoxy group was blockedto prevent crosslinking reaction of the both functional groups under thestorage condition.

In Comparative example 21, as shown in Table 17, viscosity increasedremarkably with the period of storage, leading finally to gellationafter 2 days, because the organometallic compound was not the thermallatent type compound and the regeneration of free carboxyl group and thecrosslinking reaction between the carboxyl group and the epoxy grouptook place.

Weathering resistance was evaluated by the same method as in Table 6.

                  TABLE 16                                                        ______________________________________                                        Comparative example   20      21                                              ______________________________________                                        compounding recipe in weight parts                                            polycarboxylic acid A-4 (a)                                                                         33.3    --                                              compound A-4          --      50.0                                            compound B-1          100     100                                             Modaflow              0.1     0.1                                             catalyst F-1          3.8     --                                              zinc octanoate        --      0.9                                             xylene                2.0     3.0                                             n-butyl acetate       0.5     0.8                                             ______________________________________                                    

                  TABLE 17                                                        ______________________________________                                        Comparative example                                                                          20           21                                                ______________________________________                                        compound (A)   polycarboxylic                                                                             A-4                                                              acid A-4 (a)                                                   compound (B)   B-2          B-2                                                              epoxy group  epoxy group                                       acid catalyst (F)                                                                            F-1          zinc octanoate                                    ratio of                                                                      mixing solid                                                                  components                                                                    (A)            28.6         37.1                                              (B)            71.4         62.9                                              content of (F) (weight %)                                                                    2.68         1.11                                              100 × (F)/{(A) + (B)}                                                   storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0          1.0                                               (poise)                                                                       viscosity after                                                                              gel after 5 days                                                                           gel after 2 days                                  30 days (poise)                                                               curing condition                                                                             120° C. × 30 min                                                              120° C. × 30 min                     properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good         good                                              acid resistance 2                                                                            good         good                                              acid resistance 3                                                                            good         good                                              impact resistance                                                                            good         good                                              weathering     good         good                                              resistance                                                                    Knoop hardness 11.1         11.5                                              ______________________________________                                         .sup.1) good: no change was observed.                                    

EXAMPLES 30 TO 47

Thermal latent acid catalysts F-5 to F-22 were prepared by the followingmethod.

Into test tubes, 10 weight parts each of the mixed solvent of methylisobutyl ketone and ethyl acetate in 1/1 weight ratio were charged andthe components for the thermal latent acid catalysts shown in Table 18were added to the solutions under stirring. The test tubes were leftstanding for 3 hours and, after ,removing the solvent in vacuo, thermallatent acid catalysts F-5 to F-21 were obtained in amounts and yieldsshown in Table 18.

                  TABLE 18                                                        ______________________________________                                        (Part 1)                                                                      Example        30     31     32   33   34   35                                ______________________________________                                        thermal latent acid catalyst                                                                 F-5    F-6    F-7  F-8  F-9  F-10                              compounding recipe in                                                         weight parts                                                                  Lewis acid                                                                    zinc chloride  1.36   1.36   1.36 1.36 1.36 1.36                              zinc bromide   --     --     --   --   --   --                                Bronsted                                                                      acid salt                                                                     acid                                                                          2-ethylhexanoic                                                                              1.44   1.44   1.44 --   --   --                                acid                                                                          (2-ethylhexyl) --     --     --   1.76 1.76 1.76                              phosphate                                                                     di(2-ethylhexyl)                                                                             --     --     --   --   --   --                                sulfosuccinic acid                                                            base                                                                          triethylamine  1.01   --     --   1.01 --   --                                N-methyl-      --     1.01   --   --   1.01 --                                morpholine                                                                    pyridine       --     --     0.79 --   --   0.79                              solvent                                                                       methyl isobutyl                                                                              5.0    5.0    5.0  5.0  5.0  5.0                               ketone                                                                        ethyl acetate  5.0    5.0    5.0  5.0  5.0  5.0                               yield (weight part)                                                                          3.6    3.7    3.5  3.6  3.8  3.7                               yield (%)      94     97     97   97   92   95                                ______________________________________                                        (Part 2)                                                                      Example        36     37     38   39   40   41                                ______________________________________                                        thermal latent acid catalyst                                                                 F-11   F-12   F-13 F-14 F-15 F-16                              compounding recipe in                                                         weight parts                                                                  Lewis acid                                                                    zinc chloride  1.36   1.36   1.36 --   --   --                                zinc bromide   --     --     --   2.25 2.25 2.25                              Bronsted                                                                      acid salt                                                                     acid                                                                          2-ethylhexanoic                                                                              --     --     --   1.44 1.44 1.44                              acid                                                                          (2-ethylhexyl) --     --     --   --   --   --                                phosphate                                                                     di(2-ethylhexyl)                                                                             4.23   4.23   4.23 --   --   --                                sulfosuccinic acid                                                            base                                                                          triethylamine  1.01   --     --   1.01 --   --                                N-methyl-      --     1.01   --   --   1.01 --                                morpholine                                                                    pyridine       --     --     0.79 --   --   0.79                              solvent                                                                       methyl isobutyl                                                                              5.0    5.0    5.0  5.0  5.0  5.0                               ketone                                                                        ethyl acetate  5.0    5.0    5.0  5.0  5.0  5.0                               yield (weight part)                                                                          5.8    5.5    5.1  4.1  4.2  4.1                               yield (%)      88     83     80   87   89   92                                ______________________________________                                        (Part 3)                                                                      Example        42     43     44   45   46   47                                ______________________________________                                        thermal latent acid catalyst                                                                 F-17   F-18   F-19 F-20 F-21 F-22                              compounding recipe in                                                         weight parts                                                                  Lewis acid                                                                    zinc chloride  --     --     --   --   --   --                                zinc bromide   2.25   2.25   2.25 2.25 2.25 2.25                              Bronsted                                                                      acid salt                                                                     acid                                                                          2-ethylhexanoic                                                                              --     --     --   --   --   --                                acid                                                                          (2-ethylhexyl) 1.76   1.76   1.76 --   --   --                                phosphate                                                                     di(2-ethylhexyl)                                                                             --     --     --   4.23 4.23 4.23                              sulfosuccinic acid                                                            base                                                                          triethylamine  1.01   --     --   1.01 --   --                                N-methyl-      --     1.01   --   --   1.01 --                                morpholine                                                                    pyridine       --     --     0.79 --    --  0.79                              solvent                                                                       methyl isobutyl                                                                              5.0    5.0    5.0  5.0  5.0  5.0                               ketone                                                                        ethyl acetate  5.0    5.0    5.0  5.0  5.0  5.0                               yield (weight part)                                                                          4.5    4.0    3.9  6.5  6.0  5.9                               yield (%)      90     80     81   87   80   81                                ______________________________________                                    

EXAMPLES 48 TO 57

These examples show application of the composition to one coat solidcolor coating.

(1) Preparation of Coating Material

Components summarized in Table 19 were utilized for the preparation ofthe coating materials. A part of or all materials were charged into asand mill and dispersed until the particle size decreased to not morethan 10 μm. Materials excluding following components were charged intothe sand mill: Denacol EX-421 in Example 48, the compound B-2 in Example49, Chemitite PZ-33 in Example 50, the compound A-4 in Example 51,Coronate EH in Example 52, Cymel 303 in Example 53, the compound B-1 inExample 54, KR-214 in Example 55 and Cymel 303 in Example 57. All theraw materials were charged into the sand mill in Example 56. In Examples48 to 55 and Example 57, one component coating compositions wereprepared by adding the materials which were not treated by the sand millto the materials treated by the sand mill. In Example 56, the materialstreated by the sand mill were utilized for the preparation of onecomponent coating composition. The coating compositions prepared werediluted with thinner (a mixture of xylene and butyl acetate in 8 to 2weight ratio) to the viscosity of 1 poise (measured by Brookfield typeviscometer at 20° C.) and stored in a sealed condition at 50° C. Afterthe coating compositions were stored for 30 days at 50° C., viscositywas measured. The results summarized in Table 20 show that the increaseof viscosity was very slight in all cases and that the coating materialshad excellent storage stability.

(2) Preparation of Test Piece

Cationic electrodeposit paint AQUA No.4200® (a product of NOFCORPORATION) was applied by electrodeposition to a soft steel platetreated with zinc phosphate in an amount to form a film having driedthickness of 20 μm and the coated plate was baked at 175° C. for 25minutes. Intermediate coating paint EPICO No.1500CP Sealer® (a productof NOF CORPORATION) was applied to the prepared plate by air spraying inan amount to form a film having dried thickness of 40 μm and the platewas baked at 140° C. for 30 minutes to obtain a base test piece.

The raw coating materials prepared in (1) were diluted with thinner (amixture of xylene and butyl acetate in 8 to 2 ratio) to a viscosityrequired for spraying (25 seconds at 20° C. by Ford cup No. 4) andapplied to the base test piece prepared before by air spray coating.Test pieces were prepared by curing the coated pieces in the conditionsshown in Table 20.

Results of the evaluation of coatings are shown in Table 20. In allcases, uniform coating having good gloss were prepared. All the coatingsshowed excellent acid resistance, impact resistance, weatheringresistance and hardness.

Weathering resistance was evaluated by the same method as in Table 6.

                                      TABLE 19                                    __________________________________________________________________________    (Part 1)                                                                      Example          48  49  50  51  52  53                                       __________________________________________________________________________    compounding recipe in weight parts                                            compound A-1     100 --  --  --  100 --                                       compound A-2     --  100 --  --  --  100                                      compound A-3     --  --  100 --  --  --                                       compound A-4     --  --  --  50.0                                                                              --  --                                       compound B-1     --  --  --  100 --  --                                       compound B-2     --  100 --  --  --  --                                       compound D-1     --  --  --  --  --  --                                       compound D-2     --  --  --  --  --  --                                       EX-421           15.5                                                                              --  --  --  --  --                                       PZ-33            --  --  16.1                                                                              --  --  --                                       Coronate EH      --  --  --  --  20.0                                                                              --                                       Cymel 303        --  --  --  --  --  14.0                                     KR-214           --  --  --  --  --  --                                       titanium dioxide 52.4                                                                              80.0                                                                              52.9                                                                              56.0                                                                              56.0                                                                              51.2                                     Modaflow         0.3 0.5 0.3 0.3 0.3 0.3                                      acid catalyst F-14                                                                             2.6 4.0 --  --  --  --                                       acid catalyst F-20                                                                             --  --  4.3 --  --  --                                       acid catalyst F-15                                                                             --  2.9 2.8 2.7                                              acid catalyst F-5                                                                              --  --  --  --  --  --                                       xylene           10  20  10  15  10  10                                       n-butyl acetate  2   4   2   3   2   2                                        __________________________________________________________________________    (Part 2)                                                                      Example            54  55     56  57                                          __________________________________________________________________________    compounding recipe in weight parts                                            compound A-1       --  --     --  --                                          compound A-2       --  --     --  --                                          compound A-3       100 100    --  --                                          compound A-4       --  --     --  --                                          compound B-1       100 --     --  --                                          compound B-2       --  --     --  --                                          compound D-1       --  --     100 --                                          compound D-2       --  --     --  100                                         EX-421             --  --     --  --                                          PZ-33              --  --     --  --                                          Coronate EH        --  --     --  --                                          Cymel 303          --  --     --  10.5                                        KR-214             --  49.0   --  --                                          titanium dioxide   80.0                                                                              67.4   40.0                                                                              48.4                                        Modaflow           0.5 0.3    0.3 0.3                                         acid catalyst F-14 --  3.3    2.1 --                                          acid catalyst F-20 --  --     --  --                                          acid catalyst F-15 --  --     --  --                                          acid catalyst F-5  3.2 --     --  1.9                                         xylene             20  15     10  10                                          n-butyl acetate    4   3      2   2                                           __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________    (Part 1)                                                                      Example        48      49      50                                             __________________________________________________________________________    compound (A)   A-1     A-2     A-3                                            compound (B)   EX-421  B-2     PZ-33                                                         epoxy group                                                                           alkoxysilane                                                                          imino group                                                           group                                                  compound (D)   --      --      --                                             thermal latent acid catalyst (F)                                                             catalyst F-14                                                                         catalyst F-14                                                                         catalyst F-20                                  ratio of                                                                      mixing solid                                                                  components                                                                    (A)            78.7    54.3    78.4                                           (B)            21.3    45.7    21.6                                           (D)            --      --      --                                             content of (F) (weight %)                                                                    3.60    3.60    5.73                                           100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0     1.0     1.0                                            (poise)                                                                       viscosity after                                                                              1.1     1.2     1.3                                            30 days (poise)                                                               curing condition                                                                             120° C.                                                                    140° C.                                                                    120° C.                                                                    140° C.                                                                    120° C.                                                                    140° C.                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                     properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       acid resistance 2                                                                            stain                                                                             good                                                                              stain                                                                             good                                                                              stain                                                                             good                                       acid resistance 3                                                                            good                                                                              good                                                                              good                                                                              good                                                                              cloud                                                                             good                                       impact resistance                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       weathering     83% 87% 90% 94% 81% 85%                                        resistance                                                                    Knoop hardness 8.8 10.8                                                                              10.0                                                                              11.0                                                                              9.1 10.5                                       __________________________________________________________________________    (Part 2)                                                                      Example        51      52      53                                             __________________________________________________________________________    compound (A)   A-4     A-1     A-2                                            compound (B)   B-1     Coronate EH                                                                           Cymel 303                                                     epoxy group                                                                           isocyanate                                                                            alkylated                                                             group   aminomethylol                                                                 group                                          compound (D)   --      --      --                                             thermal latent acid catalyst (F)                                                             catalyst F-15                                                                         catalyst F-15                                                                         catalyst F-15                                  ratio of                                                                      mixing solid                                                                  components                                                                    (A)            37.1    74.1    81.1                                           (B)            62.9    25.9    18.9                                           (D)            --      --      --                                             content of (F) (weight %)                                                                    3.60    3.60    3.60                                           100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0     1.0     1.0                                            (poise)                                                                       viscosity after                                                                              1.1     1.1     1.1                                            30 days (poise)                                                               curing condition                                                                             120° C.                                                                    140° C.                                                                    120° C.                                                                    140° C.                                                                    120° C.                                                                    140° C.                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                     properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       acid resistance 2                                                                            stain                                                                             good                                                                              stain                                                                             good                                                                              good                                                                              good                                       acid resistance 3                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       impact resistance                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       weathering     83% 86% 84% 87% 82% 86%                                        resistance                                                                    Knoop hardness 7.7 9.9 9.5 11.2                                                                              10.0                                                                              10.7                                       __________________________________________________________________________    (Part 3)                                                                      Example          54         55                                                __________________________________________________________________________    compound (A)     A-3        A-3                                               compound (B)     B-1        KR-214                                                             epoxy group                                                                              silanol group                                     compound (D)     --         --                                                thermal latent acid catalyst (F)                                                               catalyst F-5                                                                             catalyst F-14                                     ratio of                                                                      mixing solid                                                                  components                                                                    (A)              53.5       63.0                                              (B)              46.5       37.0                                              (D)              --         --                                                content of (F) (weight %)                                                                      2.92       3.60                                              100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                              1.0        1.0                                               (poise)                                                                       viscosity after  1.1        1.2                                               30 days (poise)                                                               curing conditions                                                                              120° C.                                                                    140° C.                                                                       120° C.                                                                    140° C.                                                 30 min                                                                            30 min 30 min                                                                            30 min                                        properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                              good                                                                              good   good                                                                              good                                          acid resistance 2                                                                              stain                                                                             good   stain                                                                             good                                          acid resistance 3                                                                              good                                                                              good   good                                                                              good                                          impact resistance                                                                              good                                                                              good   good                                                                              good                                          weathering       81% 85%    88% 93%                                           resistance                                                                    Knoop hardness   8.2 10.4   8.7 10.5                                          __________________________________________________________________________    (Part 4)                                                                      Example          56         57                                                __________________________________________________________________________    compound (A)     --         --                                                compound (B)     --         Cymel 303                                                                     alkylated amino--                                                             methylol group                                    compound (D)     D-1        D-2                                                                epoxy group                                                                              bydroxyl group                                                     alkoxysilane group                                           thermal latent acid catalyst (F)                                                               catalyst A catalyst D                                        ratio of                                                                      mixing solid                                                                  components                                                                    (A)              --         --                                                (B)              --         16.0                                              (D)              100        84.0                                              content of (F) (weight %)                                                                      3.60       2.92                                              100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                              1.0        1.0                                               (poise)                                                                       viscosity after  1.1        1.2                                               30 days (poise)                                                               curing conditions                                                                              120° C.                                                                    140° C.                                                                       120° C.                                                                    140° C.                                                 30 min                                                                            30 min 30 min                                                                            30 min                                        properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                              good                                                                              good   good                                                                              good                                          acid resistance 2                                                                              stain                                                                             good   stain                                                                             good                                          acid resistance 3                                                                              good                                                                              good   good                                                                              good                                          impact resistance                                                                              good                                                                              good   good                                                                              good                                          weathering       82% 87%    81% 85%                                           resistance                                                                    Knoop hardness   9.5 11.3   10.2                                                                              10.8                                          __________________________________________________________________________     .sup.1) good: no change was observed; stain: slight stain was observed;       cloud: surface was slightly cloudy.                                      

EXAMPLES 58 TO 64

These examples show application of the composition to two coat one bakemetallic color coating.

(1) Preparation of Clear Coating Compositions

One component clear coating compositions were prepared by mixing rawmaterials shown in Table 21. The clear coating compositions preparedwere evaluated on storage stability by the same method as in Example 48through 57. As shown in Table 22, increase of viscosity was very slightin all cases tested and coating materials were shown to have excellentstorage stability.

2) Preparation of Test Pieces

Raw coating materials thus prepared were diluted by the same method asin Examples 48 through 57. Base test pieces were also prepared by thesame method as in Examples 48 through 57. A silver metallic base coatingcomposition BELCOAT No.6000® (a product of NOF CORPORATION) was appliedto the base test piece by air spraying with interval of 1 minute 30seconds in 2 stages in an amount to form a film having dried thicknessof 15 μm. After the test piece was set at 20° C. for 3 minutes, thediluted raw clear coating compositions were coated by air spray coatingand the test pieces were cured in the condition shown in Table 22 toprepare final test pieces.

Results of evaluation listed in Table 22 show that, in all cases,uniform coating films having good gloss were prepared and the coatingshowed excellent acid resistance, impact resistance, weatheringresistance and hardness.

Weathering resistance was evaluated by the same method as in Table 6.

                                      TABLE 21                                    __________________________________________________________________________    Example          58  59  60  61  62  63  64                                   __________________________________________________________________________    compounding recipe in weight parts                                            compound A-2     100 --  --  --  --  --  --                                   compound A-4     --  50  --  --  50  50  50                                   compound B-1     --  100 --  --  100 100 100                                  compound B-2     100 --  --  --  --  --  --                                   compound D-1     --  --  100 --  --  --  --                                   compound D-2     --  --  --  100 --  --  --                                   Cymel 303        --  --  --  10.5                                                                              --  --  --                                   Modaflow         0.2 0.1 0.1 0.1 0.1 0.1 0.1                                  xylene           5   4   3   3   4   4   4                                    n-butyl acetate  1   1   1   1   1   1   1                                    acid catalyst F-14                                                                             4.0 --  --  --  --  --  --                                   acid catalyst F-20                                                                             --  4.6 --  --  --  --  --                                   acid catalyst F-15                                                                             --  --  2.1 1.9 --  4.6 2.9                                  acid catalyst F-5                                                                              --  --  --  --  2.4 --  --                                   __________________________________________________________________________

                                      TABLE 22                                    __________________________________________________________________________    (Part 1)                                                                      Example          58         59                                                __________________________________________________________________________    compound (A)     A-2        A-4                                               compound (B)     B-2        B-1                                                                alkoxysilane group                                                                       epoxy group                                       compound (D)     --         --                                                thermal latent acid catalyst (F)                                                               catalyst F-14                                                                            catalyst F-20                                     ratio of                                                                      mixing solid                                                                  components                                                                    (A)              54.3       37.1                                              (B)              45.7       62.9                                              (D)              --         --                                                content of (F) (weight %)                                                                      3.60       5.73                                              100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                              1.0        1.0                                               (poise)                                                                       viscosity after  1.2        1.1                                               30 days (poise)                                                               curing conditions                                                                              120° C.                                                                    140° C.                                                                       120° C.                                                                    140° C.                                                 30 min                                                                            30 min 30 min                                                                            30 min                                        properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                              good                                                                              good   good                                                                              good                                          acid resistance 2                                                                              good                                                                              good   good                                                                              good                                          acid resistance 3                                                                              good                                                                              good   good                                                                              good                                          impact resistance                                                                              good                                                                              good   good                                                                              good                                          weathering       good                                                                              good   good                                                                              good                                          resistance                                                                    Knoop hardness   10.8                                                                              11.1   10.2                                                                              11.1                                          __________________________________________________________________________    (Part 2)                                                                      Example          60         61                                                __________________________________________________________________________    compound (A)     --         --                                                compound (B)     --         Cymel 303                                                                     alkylated amino-                                                              methylol group                                    compound (D)     D-1        D-2                                                                epoxy group                                                                              hydroxyl group                                                     alkoxysilane group                                           thermal latent acid catalyst (F)                                                               catalyst F-15                                                                            catalyst F-15                                     ratio of                                                                      mixing solid                                                                  components                                                                    (A)              --         --                                                (B)              --         16.0                                              (D)              100        84.0                                              content of (F) (weight %)                                                                      3.60       2.92                                              100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                              1.0        1.0                                               (poise)                                                                       viscosity after  1.1        1.1                                               30 days (poise)                                                               curing conditions                                                                              120° C.                                                                    140° C.                                                                       120° C.                                                                    140° C.                                                 30 min                                                                            30 min 30 min                                                                            30 min                                        properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                              good                                                                              good   good                                                                              good                                          acid resistance 2                                                                              good                                                                              good   good                                                                              good                                          acid resistance 3                                                                              good                                                                              good   good                                                                              good                                          impact resistance                                                                              good                                                                              good   good                                                                              good                                          weathering       good                                                                              good   good                                                                              good                                          resistance                                                                    Knoop hardness   10.1                                                                              10.5   10.4                                                                              11.0                                          __________________________________________________________________________    (Part 3)                                                                      Example        62      63      64                                             __________________________________________________________________________    compound (A)   A-4     A-4     A-4                                            compound (B)   B-1     B-1     B-1                                                           epoxy group                                                                           epoxy group                                                                           epoxy group                                    compound (D)   --      --      --                                             thermal latent acid catalyst (F)                                                             catalyst F-5                                                                          catalyst F-20                                                                         catalyst F-15                                  ratio of                                                                      mixing solid                                                                  components                                                                    (A)            37.1    37.1    37.1                                           (B)            62.9    62.9    62.9                                           (D)            --      --      --                                             content of (F) (weight %)                                                                    2.92    5.73    3.60                                           100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (50° C.)                                                               initial viscosity                                                                            1.0     1.0     1.0                                            (poise)                                                                       viscosity after                                                                              1.4     1.3     1.2                                            30 days (poise)                                                               curing condition                                                                             120° C.                                                                    140° C.                                                                    120° C.                                                                    140° C.                                                                    120° C.                                                                    140° C.                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                                                            30 min                                     properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       acid resistance 2                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       acid resistance 3                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       impact resistance                                                                            good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       weathering     good                                                                              good                                                                              good                                                                              good                                                                              good                                                                              good                                       resistance                                                                    Knoop hardness 11.2                                                                              11.9                                                                              10.0                                                                              10.9                                                                              9.9 10.7                                       __________________________________________________________________________     .sup.1) good: no change was observed.                                    

EXAMPLES 65 TO 71

Thermal latent acid catalysts F-23 to F-29 were prepared by thefollowing method.

Into test tubes, 10 weight parts each of ethyl acetate were charged andthe components for the thermal latent acid catalysts shown in Table 23were added to the solutions under stirring. The test tubes were leftstanding for 3 hours and, after removing the solvent by distillation,thermal latent acid catalysts F-23 to F-29 shown in Table 23 wereobtained.

Methyl phosphate shown in Table 23 is a mixture of monomethyl phosphateand dimethyl phosphate.

                  TABLE 23                                                        ______________________________________                                        Example     65     66     67   68   69   70   71                              ______________________________________                                        thermal latent                                                                            F-23   F-24   F-25 F-26 F-27 F-28 F-29                            acid catalyst                                                                 compounding recipe                                                            in weight parts                                                               Lewis acid                                                                    zinc chloride                                                                             1.36   1.36   1.36 --   --   --   --                              zinc bromide                                                                              --     --     --   2.25 2.25 2.25 --                              zinc octanoate                                                                            --     --     --   --   --   --   3.52                            Bronsted acid                                                                 dodecylbenzene-                                                                           6.53   --     --   6.53 --   --   3.27                            sulfonic acid                                                                 dichloroacetic                                                                            --     2.58   --   --   2.58 --   --                              acid                                                                          methyl phosphate                                                                          --     --     1.62 --   --   1.62 --                              solvent     10.0   10.0   10.0 10.0 10.0 10.0 10.0                            ethyl acetate                                                                 yield (weight part)                                                                       7.5    3.7    2.7  8.3  4.6  3.6  6.6                             yield (%)   95     94     91   95   95   93   97                              ______________________________________                                    

EXAMPLE 72

Example of preparation of material 9; an acrylic resin comprisingcarboxyl group H-1 was synthesized by the following method.

Into a 2 l four-necked flask equipped with a cooler, a thermometer, astirrer and a dropping funnel, 488 weight parts of methyl isobutylketonewere charged and heated to 100° C. To the heated solvent, a mixture of77 weight parts of methacrylic acid, 194 weight parts of methylmethacrylate, 221 weight parts of n-butyl acrylate and 20 weight partsof 2,2'-azo-bis-isobutyronitrile was dropped during 2 hours and thereaction mixture was kept at 100° C. for further 2.5 hours for reactionto obtain a solution containing resin H-1 having the acid value of 100mg KOH/g, the solid content of 51.6 weight % and the number averagemolecular weight of 3000.

To a mixture of 100 weight parts of the solution of polycarboxylic acidH-1, 11.9 weight parts of an epoxy hardener ERL-4221 (a product of UnionCarbide Co.) and 45 weight parts of xylene, 3.85 weight parts of thethermal latent acid catalyst F-23 prepared in Example 65 were added toprepare a thermosetting composition. The thermosetting composition wasapplied to a piece of tinplate by flow coating and baked at 140° C. for30 minutes. Knoop hardness of the coating was measured to evaluate thecatalytic activity of a catalyst. Number of day elapsed until gellationof a thermosetting composition on storage at 30° C. was measured toevaluate the thermal latent ability of a catalyst. Compositions of thethermosetting compositions used and results of the evaluation are shownin Table 24.

                                      TABLE 24                                    __________________________________________________________________________    Example                   72  73  74  75  76   77  78  --  --                 Comparative example       --  --  --  --  --   --  --  22  23                 __________________________________________________________________________    composition of thermosetting composition (weight part)                        resin solution of         100 100 100 100 100  100 --  100 100                Example of preparation                                                        of material 1                                                                 ERL-4221                  11.9                                                                              11.9                                                                              11.9                                                                              11.9                                                                              11.9 11.9                                                                              --  11.9                                                                              11.9               xylene                    45  45  45  45  45   45  --  45  45                 thermal latent                                                                acid catalyst                                                                 F-23                      3.85                                                                              --  --  --  --   --  --  --  --                 F-24                      --  1.91                                                                              --  --  --   --  --  --  --                 F-25                      --  --  1.45                                                                              --  --   --  --  --  --                 F-26                      --  --  --  4.27                                                                              --   --  --  --  --                 F-27                      --  --  --  --  2.35 --  --  --  --                 F-28                      --  --  --  --  --   1.88                                                                              --  --  --                 F-29                      --  --  --  --  --   --  3.29                                                                              --  --                 zinc chloride             --  --  --  --  --   --  --  --  0.66               properties                                                                    Knoop hardness 11         11  11  10  11  11   10  11  7   11                 time to gellation         45  40  49  42  41   47  50  53  1                  at 30° C. (day)                                                        __________________________________________________________________________

EXAMPLES 73 TO 78

Thermosetting compositions were prepared by using thermal latent acidcatalysts prepared in Examples 66 to 71 and evaluated by the same methodas in Example 69. Results are shown in Table 24.

COMPARATIVE EXAMPLE 22

A thermosetting composition was prepared and evaluated by the samemethod as in Example 69 except that no thermal latent acid catalyst wasused. Results are shown in Table 24.

COMPARATIVE EXAMPLE 23

A thermosetting composition was prepared and evaluated by the samemethod as in Example 69 except that zinc chloride was used inComparative example 23 in place of the thermal latent acid catalyst inExample 69. Results are shown in Table 24.

The results in Table 24 show that the thermosetting compositions usingthe thermal latent acid catalysts of the invention had excellent storagestability and sufficient curing reactivity simultaneously while thethermosetting composition containing no thermal latent acid catalyst inComparative example 22 showed insufficient curing though it had goodstorage stability and the thermosetting composition containing zincchloride catalyst in place of the thermal latent acid catalyst inComparative example 23 showed insufficient storage stability though ithad good curing reactivity.

EXAMPLES 79 TO 81

These examples show application of the composition to two coat one bakemetallic color coating.

(1) Preparation of Clear Coating Compositions

One component clear coating compositions were prepared by mixing rawmaterials shown in Table 25 and evaluated on storage stability at 30° C.As shown in Table 26, increase of viscosity was very slight in all casestested and coating materials were shown to have excellent storagestability.

2) Preparation of Test Pieces

Raw coating materials thus prepared were diluted by the same method asin Examples 1 to 11. Base test pieces were also prepared by the samemethod as in Examples 1 to 11. A silver metallic base coatingcomposition BELCOAT No.6000® (a product of NOF CORPORATION) was appliedto the base test piece by air spraying with interval of 1 minute 30seconds in 2 stages in an amount to form a film having dried thicknessof 15 μm. After the test piece was set at 20° C. for 3 minutes, thediluted raw clear coating compositions were coated by air spray coatingand the test pieces were cured in the condition shown in Table 26 toprepare final test pieces.

Results of evaluation listed in Table 26 show that, in all cases,uniform coating films having good gloss were prepared and the coatingshowed excellent acid resistance, impact resistance, weatheringresistance and hardness.

Weathering resistance was evaluated by the same method as in Table 6.

                  TABLE 25                                                        ______________________________________                                        Example            79       80      81                                        ______________________________________                                        compounding recipe in weight parts                                            compound A-2       100      --      --                                        compound A-4       --       50.0    --                                        compound B-2       100      --      --                                        compound B-1       --       100     --                                        compound D-1       --       --      100                                       Modaflow           0.2      0.1     0.1                                       catalyst F-29      5.75     4.2     3.0                                       xylene             3.5      3.0     2.0                                       n-butyl acetate    0.9      0.8     0.5                                       ______________________________________                                    

                                      TABLE 26                                    __________________________________________________________________________    Example        79        80       81                                          __________________________________________________________________________    compound (A)   A-2       A-4      --                                          compound (B)   B-2       B-1      --                                                         alkoxysilane group                                                                      epoxy group                                          compound (D)   --        --       D-1                                                                           epoxy group                                                                   alkoxysilane group                          acid catalyst (F)                                                                            F-29      F-29     F-29                                        ratio of                                                                      mixing solid                                                                  components                                                                    (A)            54.3      37.1     --                                          (B)            45.7      62.9     --                                          (D)            --        --       100                                         content of (F) (weight %)                                                                    5.21      5.21     5.21                                        100 × (F)/{(A) + (B) + (D)}                                             storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                            1.0       1.0      1.0                                         (poise)                                                                       viscosity after                                                                              1.2       1.1      1.2                                         30 days (poise)                                                               curing condition                                                                             120° C. × 30 min                                                           120° C. × 30 min                                                          120° C. × 30 min               properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                            good      good     good                                        acid resistance 2                                                                            good      good     good                                        acid resistance 3                                                                            good      good     good                                        impact resistance                                                                            good      good     good                                        weathering     good      good     good                                        resistance                                                                    Knoop hardness 11.3      12.1     12.0                                        __________________________________________________________________________     .sup.1) good: no change was observed.                                    

EXAMPLES 82 TO 85

Compounds having oxazoline group were applied by the following method.

(1) Preparation of Clear Coating Material

Components summarized in Table 27 were utilized for the preparation ofthe one component clear coating materials. The clear coatingcompositions prepared were diluted with thinner (a mixture of xylene andbutyl acetate in 8 to 2 weight ratio) to the viscosity of 1 poise(measured by Brookfield type viscometer at 20° C.) and stored in asealed condition at 30° C. After the coating compositions were storedfor 30 days at 30° C., viscosity was measured. The results summarized inTable 27 show that the increase of viscosity was very slight in allcases and that the coating materials had excellent storage stability.

(2) Preparation of Test Piece

Cationic electrodeposit paint AQUA No.4200® (a product of NOFCORPORATION) was applied by electrodeposition to a soft steel platetreated with zinc phosphate in an amount to form a film having driedthickness of 20 μm and the coated plate was baked at 175° C. for 25minutes. Intermediate coating paint EPICO No.1500CP Sealer® (a productof NOF CORPORATION) was applied to the prepared plate by air spraying inan amount to form a film having dried thickness of 40 μm and the platewas baked at 140° C. for 30 minutes to obtain a base test piece.

The raw coating materials prepared in (1) were diluted with thinner (amixture of xylene and butyl acetate in 8 to 2 ratio) to a viscosityrequired for spraying (25 seconds at 20° C. by Ford cup No. 4) andapplied to the base test piece prepared before by air spray coating.Test pieces were prepared by curing the coated pieces in the conditionsshown in Table 27.

Results of the evaluation of coatings are shown in Table 27. In allcases, uniform coating having good gloss were prepared. All the coatingsshowed excellent acid resistance, impact resistance, weatheringresistance and hardness.

Weathering resistance was evaluated by the same method as in Table 6.

                  TABLE 27                                                        ______________________________________                                        Example          82      83      84    85                                     ______________________________________                                        compounding recipe in                                                         weight parts                                                                  thermal latent carboxyl                                                                        29.4    29.4    29.4  29.4                                   compound A-5 in Example of                                                    preparation of material 4 (3)                                                 CX-RS-1200       100     100     --    --                                     CX-RS-3200       --      --      100   100                                    acid catalyst A  15.4    --      15.4  --                                     acid catalyst B  --      6.3     --    6.3                                    storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity                                                                              0.9     0.9     0.9   0.9                                    (poise)                                                                       viscosity after  1.7     1.8     1.7   1.8                                    30 days (poise)                                                               properties of                                                                 coating.sup.1)                                                                acid resistance 1                                                                              good    good    good  good                                   acid resistance 2                                                                              good    good    good  good                                   acid resistance 3                                                                              good    good    good  good                                   impact resistance                                                                              good    good    good  good                                   weathering       85%     83%     88%   84%                                    resistance                                                                    Knoop hardness   7.0     11.9    10.2  13.6                                   ______________________________________                                         .sup.1) good: no change was observed.                                    

COMPARATIVE EXAMPLES 24 AND 25

Clear coating materials were prepared by using materials of thecompositions shown in Table 28 and evaluated on storage stability by thesame method as in Examples 82 to 85. The clear coating materialsprepared here all gelled after 14 days because they comprised no thermallatent carboxylic acid.

                  TABLE 28                                                        ______________________________________                                        Comparative example                                                                              24       25                                                ______________________________________                                        compounding recipe in weight parts                                            thermal latent carboxyl                                                                          24.6     24.6                                              compound A-4(a) in Example of                                                 preparation of material 4 (1)                                                 CX-RS-1200         100      --                                                CX-RS-3200         --       100                                               acid catalyst B    6.3      6.3                                               storage                                                                       stability                                                                     (30° C.)                                                               initial viscosity  0.9      0.9                                               (poise)                                                                       viscosity after    gel after                                                                              gel after 14 days                                 30 days (poise)    14 days                                                    properties of                                                                 coating.sup.1)                                                                acid resistance 1  good     good                                              acid resistance 2  good     good                                              acid resistance 3  good     good                                              impact resistance  good     good                                              weathering         81%      85%                                               resistance                                                                    Knoop hardness     11.8     12.5                                              ______________________________________                                         .sup.1) good: no change was observed.                                    

While the invention has been particularly shown and described withreference to preferred embodiments thereof, it will be understood bythose skilled in the art that the foregoing and other changes in formand details can be made therein without departing from the spirit andscope of the invention.

To summarize the advantages obtained by the invention, the thermosettingcomposition of the invention gives cured products having excellentchemical properties, physical properties, weathering resistance andstorage stability and is advantageously utilized for coatingcompositions, ink, adhesive and molded plastics. Particularly when it isutilized as a top coat material, it discharges little amount of organicsolvents into air, gives excellent appearance to the finished articlesand is advantageously applied to the field of industrial coating such ascoating of automobiles.

The thermal latent acid catalyst of the invention has excellent storagestability and heat curing reactivity when it is applied to thethermosetting composition and advantageously utilized.

What is claimed is:
 1. A thermosetting composition which comprises:(A) acompound having in the molecule two or more functional groups of theformula (1): ##STR13## wherein R¹, R² and R³ are respectively selectedfrom the group consisting of a hydrogen atom and an organic group of 1to 18 carbon atoms, R⁴ is an organic group of 1 to 18 carbon atoms, Y¹is selected from the group consisting of an oxygen atom and a sulfuratom and R³ and R⁴ may be bonded with each other to form a heterocyclicstructure which comprises Y¹ as the hereto atom component; (B) acompound having in the molecule two or more reactive functional groupswhich can form a chemical bond with the functional groups of thecompound (A) by heating, the reactive functional groups of the compound(B) are at least one kind selected from the group consisting of epoxygroup, silanol group, alkoxysilane group, hydroxyl group, amino group,imino group, isocyanate group, blocked isocyanate group, cyclocarbonategroup, vinyl ether group, vinyl thioether group, aminomethylol group,alkylated aminomethylol group, acetal group and ketal group; and,optionally, (C) a thermal latent acid catalyst which is activated duringcuring of the composition by heating.
 2. The thermosetting compositionas claimed in claim 1 wherein the thermal latent acid catalyst (C) is atleast one kind selected from the group consisting of a compound preparedby neutralizing a protonic acid or a Lewis acid with a Lewis base, anester of a sulfonic acid, an ester of phosphoric acid and an ,oniumcompound or a compound prepared by mixing a Lewis acid with trialkylphosphate.
 3. The thermosetting composition as claimed in claim 2,wherein the compound (A) and/or the compound (B) are polymers ofα,β-unsaturated compounds.
 4. The thermosetting composition as claimedin claim 2, wherein the compound (A) and/or the compound (B) arepolyester resins.
 5. The thermosetting composition as claimed in claim1, wherein the compound (A) and/or the compound (B) are polymers ofα,β-unsaturated compounds.
 6. The thermosetting composition as claimedin claim 1, wherein the thermal latent acid catalyst (C) is at least onekind selected from the group consisting of a compound prepared byneutralizing a protonic acid or a Lewis acid with a Lewis base, an esterof a sulfonic acid, an ester of phosphoric acid and an onium compound ora compound prepared by mixing a Lewis acid with trialkyl phosphate. 7.The thermosetting composition as claimed in claim 1, wherein thecompound (A) and the compound (B) are polymers of α,β-unsaturatedcompounds.
 8. The thermosetting composition as claimed in claim 1,wherein the compound (A) and/or the compound (B) are polyester resins.9. The thermosetting composition as claimed in claim 1, wherein compound(A) is a compound prepared by the half-esterification of (i) a polyolhaving two or more hydroxyl groups in the molecule and (ii) an acidanhydride; and compound (B) is an acrylic resin having two or more epoxygroups in the molecule.
 10. The thermosetting composition as claimed inclaim 1, wherein the thermal latent acid catalyst (C) is prepared byneutralizing a Lewis acid with a Lewis base, the Lewis acid being zincoctanoate and the Lewis base being triethylphosphate.
 11. Thethermosetting composition as claimed in claim 1, wherein an equivalentratio of the functional groups of the compound (A) and the reactivefunctional groups of the compound (B) is 0.2:1.0 to 1.0:0.2.
 12. Thethermosetting composition as claimed in claim 1, wherein an amount ofthe thermal latent acid catalyst is 0.01 to 10 weight parts per 100weight parts of a total solid component of the compound (A) and thecompound (B).
 13. The thermosetting composition as claimed in claim 1,wherein the compound (A) has 2 to 50 functional groups of the formula (1 ) in the molecule.
 14. The thermosetting composition as claimed inclaim 13, wherein the compound (B) has 2 to 50 reactive functionalgroups in the molecule.
 15. The thermosetting composition as claimed inclaim 1, wherein the compound (A) is a thermal latent carboxyl compoundprepared by reaction of a polycarboxyl compound prepared by a halfesterification of a polyol having two or more hydroxyl groups in themolecule and an acid hydride with a vinyl ether compound, whereby thecarboxyl group is transformed into the functional group of the formula(1).
 16. The thermosetting composition as claimed in claim 15, whereinthe vinyl ether compound is an aliphatic vinyl ether compound having 3to 10 carbon atoms.
 17. The thermosetting composition as claimed inclaim 15, wherein the vinyl ether compound is an aliphatic vinyl ethercompound having 4 to 10 carbon atoms.
 18. The thermosetting compositionas claimed in claim 15, wherein the vinyl ether compound is selectedfrom the group consisting of methyl vinyl ether, ethyl vinyl ether,isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether,isobutyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinylether.
 19. The thermosetting composition as claimed in claim 1, whereinthe compound (B) is a compound having two or more epoxy groups in themolecule.
 20. The thermosetting composition as claimed in claim 1,wherein the compound (B) is a polymer of an α, β-unsaturated compound.21. The thermosetting composition claimed in claim 1, wherein thecompound (A) is a polymer of an α, β-unsaturated compound.
 22. A methodof coating which comprises coating a substrate with a top coatingmaterial comprising pigments and the thermosetting composition claimedin claim 1, the amount of the pigments being 0 to 100 weight parts basedon 100 weight parts of the thermosetting composition.
 23. A method ofcoating which comprises coating a substrate with a composite coatinglayer by forming a base coat on the substrate with a composition forminga colored film, followed by forming a clear top coat on the base coatwith a composition forming a clear film, the composition forming a clearfilm alone or both of the composition forming a clear film and thecomposition forming a colored film comprising the thermosettingcomposition claimed in claim
 1. 24. A method of coating which comprisescoating a substrate with a top coating material comprising pigments anda thermosetting composition, the pigments being in an amount of 0 to 100weight parts based on 100 weight parts of the thermosetting composition,wherein the thermosetting composition is as claimed in claims 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or
 21. 25. Amethod of coating which comprises coating a substrate with a compositecoating layer by forming a base coat on the substrate with a compositionforming a colored film, followed by forming a clear top coat on the basecoat with a composition forming a clear film, the composition forming aclear film alone or both of the composition forming a clear film and thecomposition forming a colored film comprising the thermosettingcomposition, wherein the thermosetting composition is as claimed inclaims 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21 or
 24. 26. A thermosetting composition which comprises:(A) a compoundhaving in the molecule two or more functional groups of the formula (1):##STR14## wherein R¹, R² and R³ are respectively selected from the groupconsisting of a hydrogen atom and an organic group of 1 to 18 carbonatoms, R⁴ is an organic group of 1 to 18 carbon atoms, Y¹ is selectedfrom the group consisting of an oxygen atom and a sulfur atom and R³ andR⁴ may be bonded with each other to form a heterocyclic structure whichcomprises Y¹ as the hetero atom component; (B) a compound having in themolecule two or more reactive functional groups which can form chemicalbonds with the functional groups of the compound (A) by heating, thereactive functional groups of the compound (B) are groups of at leastone kind selected from the group consisting of epoxy group, oxazolinegroup, silanol group, alkoxysilane group, hydroxyl group, amino group,imino group, isocyanate group, blocked isocyanate group, cyclocarbonategroup, vinyl ether group, vinyl thioether group, aminomethylol group,alkylated aminomethylol group, acetal group and ketal group; and (F) acomplex compound formed by coordination of a conjugated base of aBronsted acid or a Bronsted salt to a vacant orbital of a Lewis acid ina mol ratio of the Bronsted acid or Bronsted salt to the vacant orbitalof the Lewis acid of 0.1 to
 4. 27. A thermosetting composition asclaimed in claim 26, wherein the compound (A) and/or the compound (B)are polymers of α,β-unsaturated compounds.
 28. A thermosettingcomposition as claimed in claim 26, wherein the compound (A) and/or thecompound (B) are polyester resins.
 29. The thermosetting composition asclaimed in claim 26, wherein compound (A) is a compound prepared by ahalf-esterification of (i) a polyol having two or more hydroxyl groupsin the molecule and (ii) an acid anhydride; compound (B) is an acrylicresin having two or more epoxy groups in the molecule; and the Lewisacid is zinc octanoate.
 30. A method of coating which comprises coatinga substrate with a top coating material comprising pigments and thethermosetting composition claimed in claim 26, claim 27, claim 28 orclaim 29, the amount of the pigments being 0 to 100 weight parts basedon 100 weight parts of the thermosetting composition.
 31. A method ofcoating which comprises coating a substrate with a composite coatinglayer by forming a base coat on the substrate with a composition forminga colored film, followed by forming a clear top coat on the base coatwith a composition forming a clear film, the composition forming a clearfilm alone or both of the composition forming a clear film and thecomposition forming a colored film comprising the thermosettingcomposition claimed in claim 26, claim 27, claim 28 or claim
 29. 32.Thermosetting compositions which comprise: (A) a compound having in themolecule two or more functional groups of the formula [1]: ##STR15##wherein R¹, R² and R³ are respectively selected from the groupconsisting of hydrogen atom and an organic group of 1 to 18 carbonatoms, R⁴ is an organic group of 1 to 18 carbon atoms, Y¹ is selectedfrom the group consisting of an oxygen atom and a sulfur atom and R³ andR⁴ may be bonded with each other to form a heterocyclic structure whichcomprises Y¹ as the hetero atom component; (G) a compound having two ormore oxazoline groups in the molecule; and, optionally, (C) a thermallatent acid catalyst which is activated during curing of the compositionby heating.
 33. Thermosetting compositions as claimed in claim 32wherein the thermal latent acid catalyst (C) is at least one kindselected from the group consisting of a compound prepared byneutralizing a Bronsted acid or a Lewis base, a complex compound formedfrom a Lewis acid and a Bronsted acid, a complex compound formed from aLewis acid and a Bronsted salt, an ester of a sulfonic acid an ester ofphosphoric acid and an onium compound.
 34. Thermosetting compositions asclaimed in claim 32 wherein the compound (A) and/or the compound (G) arepolymers of α,β-unsaturated compounds.
 35. Thermosetting compositions asclaimed in claim 32 wherein the compound (A) and/or the compound (G) arepolyester resins.
 36. A thermosetting composition which comprises:(A) acompound having in the molecule two or more functional groups of theformula (1): ##STR16## wherein R¹, R² and R³ are respectively selectedfrom the group consisting of a hydrogen atom and an organic group of 1to 18 carbon atoms, R⁴ is an organic group of 1 to 18 carbon atoms, Y¹is selected from the group consisting of an oxygen atom and a sulfuratom and R³ and R⁴ may be bonded with each other to form a heterocyclicstructure which comprises Y¹ as the hereto atom component; (B) acompound having in the molecule two or more reactive functional groupswhich can form a chemical bond with the functional groups of thecompound (A) by heating, the reactive functional groups of the compound(B) being oxazoline groups and, optionally, (C) a thermal latent acidcatalyst which is activated during curing of the composition by heating.